TRANSITION-METAL-CATALYZED

FUNCTIONALIZATION OF
1,10-PHENANTHROLINES AND THEIR
COMPLEXES
Anton S Abel, Alexei D Averin, Irina P Beletskaya, Alla G.
Bessmertnykh-Lemeune

To cite this version:

Anton S Abel, Alexei D Averin, Irina P Beletskaya, Alla G. Bessmertnykh-Lemeune. TRANSITION-
METAL-CATALYZED FUNCTIONALIZATION OF 1,10-PHENANTHROLINES AND THEIR
COMPLEXES. Taggets in Heterocyclic Systems: Chemistry and Properties 2021, pp.419-444, 2021,
�10.17374/targets.2021.24.419�. �hal-03414821�

HAL Id: hal-03414821

https://hal.science/hal-03414821
Submitted on 4 Nov 2021

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 1
TRANSITION-METAL-CATALYZED FUNCTIONALIZATION OF 1,10-
PHENANTHROLINES AND THEIR COMPLEXES
DOI: http://dx.medra.org/10.17374/targets.xxxxxxx
Anton S. Abela, Alexei D. Averina,b, Irina P. Beletskayaa,b and Alla Bessmertnykh-Lemeunec
a
Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia
(e-mail: [email protected])
b
A .N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
Moscow, Russia
cc
ENS de Lyon, CNRS UMR 5182, Université Claude Bernard Lyon 1, Laboratoire de Chimie, 69342,
Lyon, France
(e-mail: [email protected])

Abstract. 1,10-Phenanthroline is a classical ligand in coordination chemistry which is renowned

among bidentate ligands for the generality of its stable metal complexes widely studied across many
fields of chemistry, physics, biology and medicine. In this review we provide a detailed summary of
experimental procedures which were developed to perform transition-metal-catalyzed reactions with
halo-1,10-phenanthrolines. These data are discussed using selected examples showing how these
reactions allow to expand beyond the range of available phenanthroline derivatives.

Contents
1. Introduction
2. Synthesis of halophenanthrolines
3. Transition-metal-catalyzed functionalization of 1,10-phenanthrolines
3.1. C–C coupling
3.2. C–Het coupling
3.3. Carboalkoxylation
3.4. Cyanation
4. Functionalization of metal complexes with 1,10-phenanthroline ligands
5. Conclusion
Acknowledgement
References

1. Introduction

Metal complexes with nitrogen-containing ligands (porphyrins, polyazamacrocycles, bipyridines,

phenanthrolines, dipyrromethenes and so forth) are widely studied across many fields of chemistry,
physics, biology and medicine because their diverse and attractive structural, optical, magnetic,
electrochemical and catalytic properties are promising for various analytical and technological
applications. 1,10-Phenanthrolines (Phens) (Fig 1) are among most demanding N-ligands to develop
supramolecular assemblies,1-5 DNA intercalators and DNA-cleaving reagents,6-8 sensors for cations,
anions and other small molecules,7,9-11 PDT agents,12 redox catalysts,13-17 photocatalysts18-20 and
photoactive electrodes for dye-sensitized solar cells.21 Due to a strong electronic interaction of the
Phen ligand and metal centers, the physical and chemical properties of metal complexes can be tuned
varying the substitution pattern of the heteroaromatic scaffold. Therefore, the development of synthetic
approaches to Phen chelators bearing different substituents at the heterocycle periphery or covalently
bonded to other functional sites promotes studies in many research fields.

Figure 1. Numeration of the positions in 1,10-phenanthroline.

 2
For a long time Phens were mainly prepared by multistep syntheses from aniline and quinoline
precursors.22 More recently, post–synthetic modifications of the heteroaromatic scaffold were
recognized as powerful strategies for Phen functionalizations.7 Many of these syntheses involve
chemical transformations of halogenated Phen derivatives using carbon–carbon and carbon–
heteroatom (N, P, B) bond forming reactions. 2- And 4-halo-substituted Phens are activated for
nucleophilic substitution reactions and react easily with oxygen, nitrogen or sulfur nucleophiles. In
contrast, the nucleophilic substitution of halogens located at positions 3 and 5 of the Phen core
demands the application of transition metal (TM) catalysis. Symmetrical dihalophenanthrolines can
also be obtained in good yields and transformed into corresponding difunctionalized derivatives.
Moreover, sometimes the nucleophilic substitution of one or the two halogen atoms at the heterocyclic
ring can be performed selectively that allows for the synthesis of unsymmetrically substituted
derivatives.
Taking profit of these nucleophilic substitution reactions, the substituents can be introduced at all
positions ( and positions relative to the nitrogen atom, Fig. 1) of conjugated aromatic rings
which allows systematic tuning of electronic and steric properties of these bidentate chelators.
Therefore, one can obtain Phen chelators containing both electron donor and electron deficient
substituents, molecular architectures possessing expanded conjugated systems, dyads in which Phen
residue is combined with porphyrins and another chromophore and even more sophisticated molecular
systems displaying a programmed arrangement of donor sites required in supramolecular chemistry
and polymer science.7
Among these substitution reactions, TM-mediated reactions are the most difficult to perform due
to low solubility of starting halides and a strong metal chelating ability of Phens. In this review we
critically evaluate experimental procedures which were developed to overcome these difficulties.
These data are discussed using selected examples showing how these reactions allow to expand
beyond the range of available Phen derivatives. The synthesis of halo-substituted 1,10-phenanthrolines
from commercially available compounds is also briefly reviewed as these are essential intermediate
compounds in the synthesis of Phens through TM- catalyzed reactions.

2. Synthesis of halophenanthrolines

Most of TM-catalyzed reactions suitable for Phen synthesis involve mono- and dihalo-
substituted derivatives as intermediate compounds. Synthetic approaches to these halides are specific
for each isomer. Since bromides are suitable substrates for most catalytic transformations of Phens, the
synthesis of corresponding iodides (commonly more expensive relative to bromides) is less explored.
Particular feature of Phen halides compared to aryl counterparts is a high reactivity of chlorine
located at  and  positions of the Phen core because of the electronegative nitrogen in the peripheral
aromatic rings. Moreover, chlorides can be obtained using less expensive reagents and in higher yields
than corresponding bromides. Therefore, they are commonly used as starting compounds to perform
functionalization of  and  positions of the Phen core.
2-Chloro- and 2-bromosubstituted 1,10-phenanthrolines are prepared from Phen through the
oxidation to 1-methyl-1,10-phenantrolin-4(1H)-one followed by its reaction with phosphoryl halides
(Scheme 1).23 The analogous three-step approach to 2,9-dicloro- and 2,9-dibromo-1,10-
phenanthrolines was described.24,25 Corresponding diiodide was prepared in 74% yield from 2,9-
dichloro-l,10-phenanthroline by the nucleophilic substitution of chlorine atoms (Scheme 1).26
 3
i) MeI P(O)X3
X = Cl 82%
ii) K3[Fe(CN)6] PX5 N N X = Br 54%
N N
KOH X
N Me O

Br
N
i) P(O)X3
Br X = Cl 85-99%
N N PX5 X = Br 81%
ii) tBuOK, N N
tBuOH, air O O X X
X = Cl
HI, NaI, reflux

N N
I I
74%

Scheme 1. Synthesis of 2-halo- and 2,9-dihalo-1,10-phenanthrolines.

To carry out the functionalization of Phen scaffold at positions, corresponding bromides are
most suitable intermediate compounds. 3-Bromo-1,10-phenanthroline can be obtained in 33% yield by
the bromination of Phen hydrochloride in nitrobenzene at 130°C using substoichiometric amount of
bromine (Scheme 2).27 Though this method allows the recovery of the unreacted Phen, it is enough
tedious due to inevitable separation of the product from the side 3,8- and 3,6-dibromo-1,10-
phenanthrolines by column chromatography.

Br2
Br
N N HCl nitrobenzene N N
130oC
33%

Scheme 2. Synthesis of 3-bromo-1,10-phenanthroline.

3,8-Dibromo-1,10-phenanthroline was synthesized by the bromination of Phen in 1-chlorobutane

in the presence of pyridine and sulfur monochloride (Scheme 3).28,29 The product has been subjected to
a tedious column chromatography to separate side dibromides and sulfur-containing by-products
which could disturb following catalytic reactions. When sulfur monocloride was replaced by sulfur
dichloride, the dibromide was obtained in low (14%) yield.30 However, using this catalyst, 3,5,8-
tribromo- and 3,5,6,8-tetrabromophenantrolines can be prepared in 11–19% yields after increasing the
bromine amount up to 4.8 equivalents.30

Br2
Br Br
Py, S2Cl2 or SCl2, BuCl, N N
N N
78oC
up to 75%

Scheme 3. Synthesis of 3,8-dibromo-1,10-phenanthroline.

Quite recently 3-iodo-phenanthroline was obtained in a good yield by reacting Phen with iodine in the
presence of tert-butyl hydroperoxide (Scheme 4).31 Very similar conditions were employed for the
synthesis of 3,8-diiodo-1,10-phenanthroline but the experimental procedure was not detailed (Scheme
4).32 These compounds exhibit excellent reactivity in the cross-coupling reactions and may serve as an
attractive alternative to above mentioned bromo derivatives.
 4
I2, tBuOOH
I + I I
N N H2O-MeCN, 80oC N N N N
up to 66% up to 60%

Scheme 4. Synthesis of 3-iodo- and 3,8-diiodo-1,10-phenanthrolines.

4-Chloro- and 4-bromo-1,10-phenanthrolines are available from 8-aminoquinoline (Scheme

5).33,14 The quinoline is initially treated with Meldrum’s acid in trimethyl orthoformate to obtain an
adduct that cyclizes in refluxing diphenyl ether to give the 4-hydroxyphenanthroline. Successive
treatment of 4-hydroxyphenanthroline with phosphoryl chloride or bromide affords the chloro- or
bromo-substituted Phens, respectively.
X
i) Meldrum's acid O
CH(OMe)3, reflux P(O)X3
ii) Ph2O, reflux N N
N N HN
X = Cl 95%
NH2 X = Br 79%

Scheme 5. Synthesis of 4-halo-1,10-phenanthrolines.

4,7-Dihalo-1,10-phenanthrolines were synthesized in good yields by the same procedure from

ortho-phenylenediamine (Scheme 6).34

Scheme 6. Synthesis of 4,7-dihalo-1,10-phenanthrolines.

To functionalize Phens at positions, the most suitable starting compounds are 5-bromo- and
5,6-dibromo-1,10-phenanthrolines. They can be prepared by the bromination of Phen in oleum in a
sealed vessel at 135oC (Scheme 7).35-37 Formation of the mono- or dibromo-substituted compound is
ensured by using of 0.5 or 1 equiv. of bromine, respectively.

N Br Br2 (1 equiv.) N Br2 (0.5 equiv.) N Br

H2SO4 (oleum) H2SO4 (oleum)

N Br N N
135oC, sealed tube 135oC, sealed tube

up to 60% up to 80%

Scheme 7. Synthesis of 5-bromo- and 5,6-dibromo-1,10-phenanthrolines.

Several synthetic approaches to unsymmetrically substituted di- and tribromides were reported.
26,30,38,39
Many of them give the target products yet in low yields and after laborious chromatographic
separations. However, the reaction of 2-chloro-l,10-phenanthroline hydrochloride with bromine in
nitrobenzene affords 8-bromo-2-chloro-l,10-phenanthroline in 50% yield after chromatography; some
starting material is recovered and can be recycled (Scheme 8).26 The chloride can be replaced by
iodide to give 8-bromo-2-iodo-1,10-phenanthroline in 74% yield.

Br2
Br HI, NaI Br
N N nitrobenzene N N reflux N N
HCl
Cl Cl I 74%
50%
 5

Scheme 8. Synthetic approach to 2-chloro- and 2-iodosubstituted 3-bromo-1,10-phenanthrolines.

3,5,6,8-Tetrabromophenanthroline was prepared in 52% yield after recrystallization of a crude

product obtained by reacting Phen with bromine in the presence of thionyl chloride (Scheme 9).

Br Br

Br2, SOCl2
Br Br
reflux N N
N N
52%

Scheme 9. Synthesis of 3,5,6,7-tetrabromophenanthroline.

At present time many of these halophenanthrolines are already commercially available at a

reasonable price that simplifies proceeding the TM-catalyzed reactions reviewed below.

3. Transition-metal-catalyzed functionalization of Phens

3.1 CC coupling

CC bond formation plays a central role in the organic synthesis. It is no wonder, therefore, that
transition-metal-catalyzed (TM-catalyzed) CC bond forming reactions for the modification of the
Phen backbone were widely explored. Several alternative routes are often available to prepare the
target ligand that is particularly important in chemical transformations of low soluble halo-1,10-
phenanthrolines and in the synthesis of Phens bearing reactive functional groups and residues.

Sonogashira cross-coupling

Synthesis of ethynyl-substituted Phens through the Sonogashira reaction was reported by Suffert
and Zeissel40,41 and seems to be the first Pd-catalyzed process in which halo-substituted Phens were
involved as substrates. The compact acetylene residue allows for extension of the Phen aromatic
system and could provide covalent bonding of the Phen moiety with other functional elements
ensuring the overall molecular rigidity and -conjugation. Acetylenic linkers are widely used for the
preparation of covalently linked multi-chromophore arrays, compounds for molecular electronics and
macrocyclic structures.
The Sonogashira coupling is widely applied to the synthesis of ethynyl-substituted Phens due to
its easy accomplishment and weak dependence on the nature of the substituents in alkynes. There are
over hundred examples of successful coupling of Phens with various alkyne substrates reported in
literature. Representative transformations with phenylacetylene and trimethylsilylacetylene are
summarized in Table 1. The reactions are smoothly run using classical catalytic systems like
Pd(PPh3)2Cl2 or Pd(PPh3)4 in the presence of CuI co-catalyst. The catalyst loading is usually 510
mol%, though there are examples of successful coupling after decreasing the catalyst amount to 13
mol% (entries 7, 8, 15 and 16). That 1,10-phenanthroline can bind copper ions obviously does not
hamper the reaction but additional treatment sometimes is needed to isolate the product in a good
yield.40 Diisopropylamine or triethylamine are typically used as bases and are taken in great excess
probably to compete with 1,10-phenanthroline in copper binding. 2- And 4-substituted phenanthrolines
can be synthesized from both chloro- or bromosubstituted Phens (entries 5 and 14), while for 3- and 5-
isomers, bromides are preferable starting compounds due to a lower reactivity of corresponding
chlorinated Phens (entry 1 and 9). E.g. the reaction with 5-chloro-1,10-phenanthroline with
phenylacetylene provides a low (16%) yield of the product (entry 3) while the bromide affords the
same product in 60% yield. Moreover, the reaction of the bromide with trimethylsilylacetylene can be
performed at room temperature (entry 1), though in the most cases the coupling reactions are
conducted on heating.
 6
Disubstituted Phens can be obtained through the one-pot two-step Sonogashira reaction using
dihalo-Phens as starting compounds. All symmetrical isomeric 2,9-, 3,8- and 4,7 derivatives were
obtained in high yields (entries 7, 8, 11, 12, 13, 16 and 17). When 3,8-diiodo- and 3,8-dibromo-1,10-
phenanthrolines were reacted with phenylacetylene, the target product was isolated in comparable
yields (76 and 82%, respectively; entries 12 and 13). The scope of alkyne precursors is very large and
some representative examples are summarized in Table 1 (entries 4, 6, 10 and 17). The copper-free
Sonogashira reaction was also reported by several groups (entries 6, 10 and 13). The products of the
reaction with trimethylsilylacetylene after the removal of the protecting Me3Si group can be further
introduced in the Sonogashira reaction or in the copper(I)-catalyzed azide alkyne cycloaddition
reaction (CuAAC).

Table 1. Sonogashira coupling of 1,10-phenanthrolines.

R R
Hal Hal [Pd]/L, CuI
+ R H
N N base N N

Entry Posi- Hal R Catalyst Reaction conditions Yield, Ref.

tion(s) (mol%) (%)
43
1 5 Br TMS Pd(PPh3)2Cl2 (10),CuI (11) iPr2NH, THF, rt, 24h 85
2 5 Br Ph Pd(PPh3)4 (10), CuI (10) iPr2NH, THF, 80oC, 48 h 60 44

3 5 Cl Ph Pd(PPh3)2Cl2 (15),CuI (34) Et3N, DMF, 90oC, 8 h 16 45

4 5,6 Br pyren-1-yl Pd(PPh3)4 (10), CuI (10) iPr2NH, benzene, 60oC 75 46

47
5 4 Br Ph Pd(DPPF)Cl2 (10), CuI (10) Et3N, DMF, r.t. 65
48
6 4 Cl 2,2':5',2''- Pd(PPh3)4 (10) Et3N, H2O-dioxane, reflux, 90
terthien-3'-yl 48 h
7 4,7 Br Ph Pd(PPh3)2Cl2 (3), CuI (4) Et3N, DMF, 90oC, 18 h 95 49

8 4,7 Cl Ph Pd(PPh3)2Cl2 (2), CuI (7) Et3N, DMF, 90oC, 8 h 87 45

9 3 Br TMS Pd(PPh3)2Cl2 (5), CuI (10) Et3N, benzene, 80oC, 72 h 92 50

10 3 Br pyren-1-yl Pd(PPh3)4 (15) PrNH2, 80oC, 48 h 79 37

11 3,8 Br TMS Pd(PPh3)2Cl2 (5), CuI (10) Et3N, DMF, 80oC, 72 h 88 51

52
12 3,8 Br Ph Pd(PPh3)2Cl2 (10), CuI (11) iPr2NH, DMF, reflux, 4 h 82
32
13 3,8 I Ph Pd(PPh3)4 PrNH2, reflux, 48 h 76
14 2 Cl TMS Pd(PPh3)2Cl2 (10), CuI (10) Et3N, DMF, 60oC, 12 h 60a 53

15 2,9 Cl TMS Pd(PPh3)2Cl2 (1.5), CuI (3) Et3N, DMF, 90oC, 18 h 63 54

16 2,9 Cl Ph Pd(PPh3)2Cl2 (2), CuI (4) Et3N, DMF, 90oC, 18 h 89 54

55
17 2,9 I 2-amino-5-(t- Pd(PPh3)4 (10), CuI (110) iPr2NH, THF, rt, 24 h 74
butyl)phenyl
a
The yield of deprotected product (R = H) obtained after hydrolysis of TMS group.

In less reactive dichlorides, substitution of one of two chlorine atoms was shown to be
possible,42 though the yield was modest (Scheme 10) due to competing substitution of the second
halogen atom. The target product was further introduced in the Suzuki coupling to give
unsymmetrically substituted 1,10-phenanthrolines.
 7

H CPh3 Ph B(OH)2
N N N N
Pd(PPh3)2Cl2, CuI Cl Pd(PPh3)4 Ph
N N K2CO3, DME, 80oC
Et3N, DMF, 90oC
Cl Cl Ph3C >95%
Ph3C 33%

Scheme 10. Stepwise catalytic difunctionalization of 2,9-dichloro-1,10-phenanthroline.

Suzuki-Miyaura cross-coupling

The Suzuki-Miyaura reaction was first applied to Phen derivatives by Chan’s group,56 and has
become one of the most frequently used cross-coupling reactions for the preparation of functionalized
Phens including polydentate chelators widely investigated in coordination and supramolecular
chemistry. The introduction of the aromatic and heteroaromatic fragments at different positions of the
phenanthroline scaffold allows fine tuning not only of its electron and steric properties but also of the
number and nature of external coordination sites of the ligand. Representative reactions are
summarized in Table 2.
High yields of the coupling products were obtained employing air-sensitive Pd(PPh3)4 as a
catalyst (entries 1, 4, 5, 715 and 18) but Pd(PPh3)2Cl2(entry 3) and Pd(dppf)Cl2 (entries 16 and 17)
work also well in this reaction. Moreover, the catalyst can be prepared in situ from Pd2(dba)3 and
bulky phosphine ligands (entries 2, 6 and 20). Sodium or potassium carbonates are common bases but
sometimes potassium acetate can afford the product in a higher yield.57 Water in small amounts is also
generally required, probably to form a more reactive Phen monohydrate and to accelerate the
transmetalation step of the catalytic cycle. The reaction is generally conducted using 510 mol% of
catalyst on heating under inert atmosphere. 2,9-Dichloro- and 4,7-dichloro-1,10-phenanthrolines are as
active as corresponding bromides, and the scope of aryl- and heteroarylboronic acids or their esters
suitable for this reaction is very wide. Nevertheless, it is worth noting that 2,9- substituted derivatives
can be obtained much more easily by direct Sauvage arylation of Phen.58
Coupling of dihalides can be performed regioselectively via the substitution of only one of two
halogen atoms by varying the nature and position of the halogen atoms in the aromatic scaffold. Iodine
is the most active at the oxidative addition step of the catalytic cycle, in particular being located at 
and  positions of the pyridine ring. Accordingly, the coupling of 8-bromo-2-iodo-1,10-
phenanthroline with an equimolar amount of 4-methoxyphenylborobic acid proceeds regioselectively
at the  position affording the product bearing unreacted bromine atom (Scheme 11).26
The Suzuki-Miyaura reaction of 2-chloro-9-iodo-1,10-phenanthroline also can be performed
selectively at the position if the amount of boronic acid is controlled (Scheme 11).26 Another
example of the regioselective substitution is the coupling of 5,6-dibromo-3-iodo-1,10-phenanthroline
with phenylboronic acid (Scheme 11).
These regioselective reactions can be followed by the second coupling with a boronic acid to give
unsymmetrical Phens as shown in Scheme 11 for 5,6-dibromo-3-iodo-1,10-phenanthroline.59 At the
first step, Pd(dppf)Cl2 complex was employed as a catalyst while Pd(PPh3)4 was used at the second
step; however, authors did not provide an explanation for such change of the catalyst.
 8

MeO B(OH)2 Br
Br N N
N N Pd(PPh3)4, Ba(OH)2
I DME-H2O, 80oC
51%
OMe

B(OH)2

N N
N N Pd(PPh3)4, Ba(OH)2 Cl
Cl I DME-H2O, 80oC
71%

Br Br Br Br

Ph B(OH)2
I Ph
Pd(DPPF)Cl2 ,Na2CO3 N N
N N toluene-water, 95oC
79%

B(OH)2

Me S Me

Pd(PPh3)4 ,Na2CO3
dioxane-water, 100oC

Me Me

S S

Me Me

Ph
N N
49%

Scheme 11. Regioselective Pd-catalyzed Suzuki-Miyaura reaction of iodo-substituted Phens.

 9

Table 2. Suzuki-Miyaura coupling of 1,10-phenanthrolines.

Entry Posi- Hal R Catalyst Reaction conditions Yield, Ref.

tion(s) [Pd]/L (%)
60
1 5 Br pyren-1-yl Pd(PPh3)4 Ba(OH)2, H2O-EtOH-toluene, reflux, 48 h 63
61
2 5 Br 4-(Ph2N)-Ph Pd2(dba)3/tBu3P Na2CO3, H2O-PrOH-toluene, reflux, 48 h 77
3 5 Br 2,2':6',2''-terpyri- Pd(PPh3)2Cl2 K2CO3, DMSO, 100oC, 24 h 73 62

din-4'-yl
63
4 5,6 Br 2,5-dimethylthio- Pd(PPh3)4 Na2CO3, H2O-THF, reflux 44
phen-3-yl
64
5 3,5,6,8 Br Ph Pd(PPh3)4 Na2CO3, H2O-toluene, reflux 71
6 4,7 Cl 4-tBu-Ph Pd2(dba)3/PCy3 Cs2CO3, H2O-dioxane, 100oC, 3 h 84 65

7a 4,7 Cl Ph Pd(PPh3)4 K2CO3, H2O-THF, reflux 98 66

8b 4,7 Br 4-pyridyl Pd(PPh3)4 K2CO3, H2O-dioxane, 130oC, 2 h 82 67

68
9 3 I Ph Pd(PPh3)4 K2CO3, H2O-toluene, reflux, 24 h 76
68
10 3,8 I Ph Pd(PPh3)4 K2CO3, H2O-toluene, reflux, 24 h 90
69
11 3 Br 4-MeO-Ph Pd(PPh3)4 Na2CO3, H2O-EtOH-toluene, reflux, 24 h 90
12 3 Br thiophen-3-yl Pd(PPh3)4 Na2CO3, EtOH-toluene, 80oC, 12 h 85 70

71
13 3,8 Br Ph Pd(PPh3)4 Na2CO3, H2O-THF-toluene, reflux, 18 h 81
72
14 2 Br thiophen-2-yl Pd(PPh3)4 Cs2CO3, H2O-dioxane, reflux, 8 h 87
15 2 Cl 4- Pd(PPh3)4 Cs2CO3, DME, 80oC, 6 h 62 73

16c 2 Cl 4-(EtO)2P(O)Ph Pd(DPPF)Cl2d Cs2CO3, dioxane, reflux, 3 h 70 74

17 2,9 Cl Ph Pd(DPPF)Cl2 Ba(OH)2, H2O-toluene, 110oC, 6 h 90 75

76
18 2,9 Cl 4-pyridyl Pd(PPh3)4 Na2CO3, H2O-DME, reflux, 20 h 84
77
19 2,9 Cl 2,6-diMeO-Ph Pd(PPh3)4 Na2CO3, H2O-DME, reflux, 20 h 83
20 2,9 Cl 3-methyl-1H- Pd2(dba)3/SPhose K3PO4, H2O-toluene ,90oC, 48 h 54 78

indol-7-yl
a
,7-Dibromo-2,9-dimethyl-1,10-phenanthroline was used. b ,7-Dichloro-2,9-dimethyl 1,10-phenanthroline was used.
c
2-Chloro-9-(4-methoxyphenyl)-1,10-phenanthroline was used. d DPPF = 1,1′-Ferrocenediyl-bis(diphenylphosphine).
e
SPhos = 2-(dicyclohexylphosphino)-2′,6′-dimethoxybiphenyl.

Regioselective substitution of only one of two identical halogen atoms in dihalophenanthrolines

was also reported. For example, 2,9-dihalo-1,10-phenanthrolines react with thienylboronic acids
affording monothienyl substituted Phens which are convenient intermediate compounds to prepare
Phens bearing two different aromatic substituents (Scheme 12).73,79
 10
(HO)2B O
S
N N
N N Pd(PPh3)4, K2CO3
DME-H2O, reflux Cl S
Cl Cl
57% O

B(OH)2 Ph2N B(OH)2

S N N
S
N N Pd(PPh3)4, Cs2CO3
N N Pd(PPh3)4, Cs2CO3
dioxane-H2O, reflux Br S toluene-H2O, reflux
Br Br
56% Ph2N 95%

Scheme 12. Regioselective Suzuki-Miyaura reactions of 2,9-dihalo-1,10-phenanthrolines and an

example of their use for preparation of unsymmetrical Phens.

Phen derivatives can also be synthesized via the Suzuki-Miyaura reaction using
phenanthrolinylboronic esters which are available from the halo-substituted Phen through the
Miyaura–Ishiyama borylation reaction. This approach is particularly attractive when homo-coupled
side products are difficult to separate by column chromatography as in the case of ditopic ligand
combining 2,9-dimethyl-1,10-phenanthroline and terpyridine structural units (Scheme 13).57

O
B O N N
Me
Pd(PPh3)2Cl2, K2CO3
+ N N N
N DMSO, 100oC
N N N N
Me Me
Br Me
65%

Scheme 13. Suzuki-Myaura coupling of phenanthrolinylboronic ester and an aryl halide.

Stille cross-coupling

The Stille reaction is an alternative to the Suzuki coupling in the synthesis of biaryls which are
widely used in the organic synthesis, but not very common in the Phen chemistry likely due to a strong
ligation of these chelators to tin(IV) organometallics.80,81 Nevertheless, this reaction also was
employed for the introduction of the substituents at all carbon atoms of the phenanthroline core. As
shown in Table 3 (entries 2, 4–6 and 9), this reaction proceeds in the presence of palladium(0)
complexes with triphenylphosphine and is convenient for the preparation of heteroaryl-substituted
phenanthrolines. For example, the introduction of thiophenyl residues (entries 2 and 4) attached
considerable interest as the corresponding starting compounds are available and the products are
required for the construction of organic electronic materials. The Stille reaction seems to be the best
pathway to vinyl-substituted Phen (entries 6 and 7) as the Mizoroki-Heck reaction in Phen series was
rarely used (see below).82,83
 11

Table 3. Stille coupling of 1,10-phenanthrolines.

Hal Hal Pd(PPh3)4 (10 mol%) R R

+ R SnR'3
N N N N

Entry Posi- Hal R’ R Reaction conditions Yield, Ref.

tion(s) (%)
1 5,6 Br Me 5-methylthiophen-2-yl DMF, 85oC, 65 h 81 84

2 4,7 Br Bu 5,5''-dialkyl-2,2':3',2''-terthien-5'-yl DMF, 110oC, 65 h 85 85

3 3,8 Br Me 4-octylthiophen-2-yl DMF, 120oC, 3 d 36 86

4a 3,8 Br nBu 2,3-dihydrothieno[3,2-b][1,4]diox- THF-DMF, 130oC, 15 h 53 87

in-6-yl
88
5 2 Br nBu 2-pyridyl toluene, reflux, 4 d 89
88
6 2 Br nBu 6-bromopyridine-2-yl toluene, reflux, 5 d 90
7 2,9 Cl nBu vinyl toluene, 110oC, 7 h 22 83

8b 2,9 Cl nBu 1-ethoxyvinyl DMF, 80oC, 60 h 69 82

89
9 2,9 Cl nBu 2-pyridyl toluene, reflux, 3 d 89
a
The catalyst was obtained by reduction of Pd(PPh3)2Cl2 with BuLi in THF. b Pd(PPh3)2Cl2 was used as a catalyst.

Negishi cross-coupling

The Negishi coupling is also not so widespread for the Phen functionalization as the Suzuki-
Miyaura reaction probably due to the formation of stable and insoluble zinc complexes with Phen
which were isolated and characterized by single crystal X-ray analysis.90 However, in some case,
purification of zinc complexes obtained in the Negishi reaction is more simple compared to the
isolation of the corresponding Phen ligands. These complexes are particularly useful in the preparation
of polydentate ligands which are difficult otherwise to purify by column chromatography. 33,91 Thus, an
important condition of successful proceeding of the Negishi coupling seems to be the engagement of
zinc dichloride in excess.
Reported examples demonstrate that the Negishi coupling being run in THF allows the
introduction of aromatic and heteroaromatic residues at all carbon atoms of the Phen scaffold using
bromo- and iodo-substituted Phens as starting compounds (Table 4, entries 1, 2, 4 and 8). Steric
hindrance of organozinc compounds does not affect the reaction outcome. However, the product yields
can be quite low as it was observed in the reactions of 4- and 5-bromo-1,10-phenantrolines with
electron rich aryl zinc derivatives (entries 1 and 2). Di- and tetrasubstitution reactions proceed
smoothly affording the target product in high yields (entries 37, 9 and 10). Moreover C(sp2)–C(sp3)
and C(sp2)–C(sp) bond formation can be achieved using organozinc compounds (entries 6 and 7,
respectively).
 12

Table 4. Negishi coupling of 1,10-phenanthrolines.

Hal Hal [Pd]/L R R

+ R ZnCl
N N base N N

Entry Posi- Hal R Catalyst Reaction conditions Yield, Ref.

tion(s) [Pd]/L (mol%) (%)
92
1 5 Br 4-(5-(4-tert-butylphenyl)- Pd(PPh3)4 (5) THF, r.t., 3 h 18
1,3,4-oxadiazol-2-yl)phenyl
91
2 4 Br 2,6-dimethyl-4-methoxy- Pd(PPh3)4 (10) THF, reflux, 15 h 15
phenyl
93
3 4,7 Br 4-CF3-phenyl « THF, reflux, 12 h 59
94
4 3,8 Br mesityl Pd(PPh3)4 (1) THF-toluene (CPhen = 71
0.08 M), 120oC, 17 h
5 3,8 Br 2,2'-bithiophen-5-yl Pd(OAc)2/PPh3(10/20) THF, 70oC, 19 h 75 95

6 3,8 Br CH2Si(Me)3 Pd(PPh3)4 (4) THF-toluene, 100oC, 3 h 64a 96

7 3,5,6,8 Br phenylethynyl CATb (20) THF, 150oC, 7h 60 90

91
8 2 I 2,6-dimethyl-4- Pd(PPh3)4 (10) THF, reflux, 15 h 69
3 Br methoxyphenyl
97
9 2,9 I 2-tiophenyl « THF, r.t., 24 h 92
10 2,9 I pentafluorophenyl Pd(OAc)2/Cy- THF, 90oC 65 98

Johnphosc (5/12)

a b
The product yield obtained after hydrolysis. CAT=

c
CyJohnphos=2-(Dicyclohexylphosphino)biphenyl.
The Negishi reaction with dihalophenanthrolines can be performed regioselectively to form
monosubstituted products. These intermediate compounds can be introduced in the Negishi or other
cross-coupling reactions to form unsymmetrical derivatives, in particular peculiar
pyridylphenanthrolines (Scheme 14).33,91 However, the reaction yields are highly dependent on the
structure of starting Phens. For example, the substitution of the -iodine by a pyridine residue in 2,9-
diiodo- and 8-bromo-2-iodo-1,10-phenanthrolines proceeds in good yields. In the case of 2,7-dibromo-
1,10-phenanthroline in which both bromo substituents are activated to the substitution being located in
 and  positions of the pyridine ring, the selectivity was not achieved; a mixture of 2- and 7-
substituted products was obtained, and the product of  substitution was isolated in only 18% yield.
Further synthetic modification using the Negishi coupling was also possible only in selected cases due
to a low solubility of Zn complexes of the intermediate compounds. The Suzuki-Miyaura coupling can
be employed to overcome this drawback as shown in Scheme 14.
 13
Ar

Y Ar ZnCl
N N
Y Ar N ZnCl N N Pd(PPh3)4 (5 mol%)
THF, reflux Y = 9-I 40% N
N N Pd(PPh3)4 (5 mol%) Y = 8-Br 79%
N Ar
X THF, reflux
Ar Ar
X = I, Y = 9-I 74% Ar B(OH)2
Ar =
X = I, Y = 8-Br 60%
N N
OMe X = Br, Y = 7-Br 18% Pd(PPh3)4 (5 mol%)
Ba(OH)2
DME-H2O, 90oC Y = 7-Br 84% N

Ar

Scheme 14. Stepwise difunctionalization of dihalo-1,10-phenanthrolines via the Negishi reaction

followed by the second coupling reaction.

Further increase of regioselectivity in the Negishi reaction of dihalophenanthrolines can be

obtained by the preparation of halo-substituted derivatives bearing different halogen atoms at the
phenanthroline core. Interesting example is 3,8-dibromo-4,7-dichloro-1,10-phenanthroline in which -
Cl substituents are activated to the substitution but bromides are known to be more reactive in the
oxidative addition step of the catalytic cycle compared to chlorides in cross-coupling reactions. The
reaction of 3,8-dibromo-4,7-dichloro-1,10-phenanthroline with mesitylene Zn derivative selectively
led to the 3,8-disubstituted product which is a valuable intermediate compound in the synthesis of
highly substituted Phen ligands (Scheme 15).

Cl Cl Cl Cl
Pd(PPh3)4 (4 mol%)
Br Br + ZnCl
THF-toluene
N N N N
120oC, 2 h
69%

Scheme 15. Negishi reaction of 3,8-dibromo-4,7-dichloro-1,10-phenanthroline via the Negishi

reaction.

It is also worth noting, that the Negishi and Sonogashira reactions can be regarded as
complimentary synthetic tools for C(sp2)–C(sp) bond formation. The Negishi coupling sometimes
gives better results compared to coupling under Sonogashira conditions as it was demonstrated
reacting 3,5,6,8-tetrabromophenanthroline with phenylacetylene.90 Employing Cl–Zn-phenylacetyl-
enide as a reagent, the yield of the target product was increased from 15% obtained in the Sonogashira
reaction, to 60%. However, a specific catalyst (see footnote of Table 4) was required for the successful
Negishi coupling (Scheme 16).

Scheme 16. Synthesis of 3,5,6,8-tetra(phenylethynyl)-1,10-phenanthroline via the Sonogashira and

Negishi reactions.
 14
Kumada cross-coupling

Quite rare is the use of the Kumada coupling in the Phen synthetic chemistry. It seems that the
better tolerance of the Suzuki-Miyaura, Negishi and Stille reactions for various functional groups
decreases the interest in this method for C–C bond formation.
It was reported that the Kumada reaction can be used for the functionalization of low reactive 3-
and 3,8-disubstituted 1,10-phenanthrolines. The reaction is conducted under classical conditions using
Ni(DPPP)Cl2 (DPPP=1,3-bis(diphenylphosphino)propane) complex as a catalyst and sometimes the
product yield can be increased by optimizing the reaction temperature. For example, Huang and co-
workers proposed to initiate the reaction at room temperature and afterwards they applied prolonged
heating.99-101 3-(Thiophen-2-yl)- and 3,8-bis(thiophen-2-yl)-substituted Phens were obtained in 73–
91% yields under these conditions. Running the reaction at room temperature resulted in lower yield
(40%) of the target product.102

R' Br Br R' Br
R S R
S N N N N
Ni(DPPP)Cl2 (2.8 mol%) R MgBr Ni(DPPP)Cl2 (2.8 mol%) N N
R S N N S
THF, reflux, 12 h THF, reflux, 12 h R'
R'
R = R' = H 94%
R = R' = H 74%
R = H, R' = CH3 82%
R = H, R' = CH3 91%
R = CH3, R' = H 73%

Scheme 17. Functionalization of Phens via the Kumada reaction.

Mizoroki-Heck cross-coupling

To our knowledge, only two examples of the Mizoroki-Heck reaction for the Phen derivatives were
reported, both by Ajibade and Adeloye.103,104 The reactions were run with trans-2,3-dimethylacrylic
acid using Pd(0) as a catalyst, and the target compounds were obtained in good yields (Scheme 18).
Br
Br Br COOH
HOOC COOH
COOH
N N N N

Pd/C, Et3N Pd/C, Et3N

N N
N N MeOH, reflux, 24 h MeOH, reflux, 8 h
53%
80%

Scheme 18. Examples of the Mizoroki-Heck reaction in Phen series.

Alternatively, vinyl-substituted Phens can be prepared in two steps from methylated Phens using
consecutive formylation and Wittig coupling reactions.105 The Stille reaction is also helpful to
synthesize these derivatives with extended aromatic system.

Reductive dimerization

Synthesis of bis-1,10-phenanthrolines was reported long ago106 and was revisited after the
development of catalytic approaches to the dimerization of aryl halides. The reported reactions of the
reductive dimerization of halo-Phens mediated by Ni(0) complexes are summarized in Table 5. 2-
Chloro-1,10-phenanthroline was the first halide of Phen series which was involved in this reaction by
Rice and Anderson107 using conditions developed for aryl chlorides by Iyoda and coworkers.108 The
reaction was conducted using NiCl2(PPh3)2 pre-catalysts in the presence of zinc dust (for reduction of
nickel(II)) and tetraethylammonium iodide in refluxed THF. The dimer was isolated in only 30% yield
which was increased more than twice after employing the nickel salt in stoichiometric amount and
performing the reaction in DMF (entries 10 and 11). Using these experimental conditions all isomeric
 15
bis-1,10-phenanthrolines as well as their alkyl- and aryl-substituted derivatives were prepared in good
yields. To note that the positive role of ammonium iodide was demonstrated for the dimerization of
various aryl chlorides108 but was not investigated in detail for Phen derivatives. Comparing the results
obtained by different groups (entries 6 and 7, 10 and 11, respectively), it seems that this additive can
be omitted at least in the preliminary experiences focusing on the preparation of unknown dimers via
this strategy.

Table 5. Ni-mediated reductive coupling of 1,10-phenanthrolines.

R’ R
N N
Hal Ni

N N reducting agent
N N
R R’
R R’

En- Posi- Hal R R’ Reagents [Ni] Reaction conditions Yield, Ref.

try tion (%)
1 5 Cl H H Zn, [Et4N]I NiCl2•6H2O/PPh3 DMF, 55oC, 14 h 71 109

(1.2/4 equiv.)
2 5 Br H H - Ni(COD)2/COD/bpya DMF, 85oC, 24 h 35 110

(1.1/1.1/1.1 equiv.)
3 5 Br Bu Bu - « DMF, 55oC, 24 h 10 110

5 4 Cl H H Zn, [Et4N]I NiCl2•6H2O/PPh3 DMF, 55oC 14 h 66 109

(1.2/4 equiv.)
6 3 Br H H Zn NiCl2/PPh3 DMF, 55oC, 70 111

(1.2/4 equiv.) overnight

7 3 Br H H Zn, [Et4N]I NiCl2•6H2O/PPh3 DMF, 55oC, 14 h 62 109

(1.2/4 equiv.)

8 3 Br Arb H Zn NiCl2•6H2O/PPh3 DMF, 50oC n/dc 112

107
9 2 Cl H H Zn, [Et4N]I NiCl2(PPh3)2 THF, reflux, 12 h 30
(10 mol%)
10 2 Cl H H Zn NiCl2/PPh3 DMF, 55oC, 80 111

(1.2/4 equiv.) overnight

11 2 Cl H H Zn, [Et4N]I NiCl2•6H2O/PPh3 DMF, 55oC,14 h 71 109

(1.2/4 equiv.)

a
COD = cycloocta-1,5-diene. b Ar = p-MeOC6H4, p-tolyl, mesityl. c n/d – not determined.

Attempts to replace NiCl2/triphenylphosphine by Ni(COD)2/COD/bpy system which works well

for 2,2’-bipyridyl derivatives113 were inconclusive because the target products were obtained in low
yields (entries 2 and 3).110 Nevertheless, these conditions were successfully applied for the synthesis of
macrocyclic ligands bearing three 1,10-phenanthroline residues in the cycle (Scheme 19).82

RO OR

RO OR
Ni(COD)2/COD/bpy N N
(2.4/2.4/2.4 equiv.)
R = C8H17 16%
DMF-toluene N N
N N R = C12H25 19%
60oC, 72 h
Cl Cl RO N N OR

RO OR
 16
Scheme 19. Synthesis of the macrocyclic ligand via the reductive trimerization of 2,9-dichloro-
1,10-phenanthroline derivatives.

It is also worth noting that Phen dimers can be obtained from halo-substituted Phens through the
tandem Miyaura /Suzuki-Miyaura coupling. This synthetic approach is still limited to rare examples
such as the dimerization of 5-bromoneocuproine (Scheme 20).114 5-Bis-1,10-neocuproine was obtained
in 78% yield by reacting this dihalide with bis(pinacolato)diboron in the presence of Pd(PPh3)2Cl2 and
potassium carbonate in DMSO at 80°C.

Br O O
B B
O O
N N

N N Pd(PPh3)2Cl2 (5 mol%)
K2CO3, DMSO, 80°C, 16 h N N

78%
Scheme 20. Synthesis of 5-bis-1,10-neocuproine according the tandem Miyaura /Suzuki-Miyaura
coupling.

3.2 CHet coupling

The CHet coupling reactions with Phens are limited to the introduction of nitrogen-, phosphorous-
and boron-containing substituents at the heterocycle.

Pd- and Cu-catalyzed amination reactions

Among Phens bearing heteroatoms directly attached to the heterocyclic core, amino-substituted
derivatives are widely investigated in sensing and supramolecular chemistry. The amination of  and 
positions of pyridine rings can be performed according the nucleophilic substitution of activated
chlorine atoms. in - or -chloro-substituted Phens However, the scope of this reaction is limited to
reactive sterically unhindered aliphatic amines. Catalytic amination reactions allow to introduce less
nucleophilic aromatic amines at these positions and they are also useful for the preparation of  and 
isomers which were inaccessible via the catalyst-free reactions. Both Cu- and Pd-catalyzed amination
reactions were reported with Phens but both required a careful optimization to obtain target products in
preparative yields.
Cu-catalyzed coupling is only used for the substitution of bromine and iodine by azole
(imidazole, pyrazole and carbazole) residues using cuprous iodide or cupric sulfate under harsh
conditions (Table 6). Soluble copper complexes which allow to perform the amination and amidation
reactions under mild conditions115,116,117 are inefficient for the functionalization of Phens probably due
to a high affinity of Phen chelators to both Cu(I) and Cu(II) ions.

Table 6. Cu-catalyzed amination of 1,10-phenanthrolines.

R R
Hal Hal R [Cu] N N
+ NH R' R'
N N R' base
N N

Entry Posi- Hal Amine Catalyst Reaction conditions Yield, Ref.

tion(s) (mol%) (%)
1 3 Br carbazole CuI (20) K2CO3, nitrobenzene 200oC, 24 h 40 118

2 3,8 Br imidazole CuSO4 (2.5) K2CO3, neat, 180oC, 4 h 70 119

3 2 I pyrazole CuI (10) K2CO3, DMSO, 100oC, 96 h 70 120

4 2 I pyrazole CuI K2CO3, DMSO, 160oC, 96 h 85 121

 17
5 2 I 2-methylimidazole CuI K2CO3, DMSO, 160oC, 96 h 77 121

6a 2 I 1,2,4-triazole CuI K2CO3, DMSO, 160oC, 96 h 62 121

a
Reaction proceeds at position 1 of the triazole.

Buchwald-Hartwig amination reaction122,123 which proceeds in the presence of palladium(0)

complexes with phosphines is a much more efficient strategy for the functionalization of Phens (Table
7). It was recognized that this catalytic cross-coupling is difficult to perform in the case of N-chelators
and heterocycles which readily coordinate transition metal ions removing them from the catalytic
cycle.124,125 Nevertheless, the reactions of Phen halides with reactive diarylamines and cyclic
secondary amines can be performed using classical Pd2(dba)3/BINAP catalytic system (entries 1, 2, 5
and 12). Other reactions demand optimization because the extensive reduction of halide is commonly
observed in the reaction mixtures. Another competing reaction which strongly influences the product
yields in the amination of -haloPhens in the presence of sodium tert-butylate is the nucleophilic
substitution affording 4-tert-butoxy-substituted Phens.
As shown in Table 7, many phosphine ligands such as tBu3P, DPPF, Xantphos (entries 8, 10 and
14) which are efficient for the amination of aryl halides can be employed for Phen functionalization.
Unfortunately, experimental conditions should be adjusted using the basic trial-and-error method. The
Josiphos ligand can be recommended for the reactions with most reluctant substrates such as sterically
hindered primary amines (entries 4 and 6) or less reactive - and -halophenanthrolines (entries 3 and
9).126 In addition, cesium carbonate seems to be the most appropriate base to perform the reaction of -
and -chloro-1,10-phenanthrolines with primary amines (entries 57).
It is of interest to compare the reaction of 4-chloro-1,10-phenanthroline with 2-(1-
adamantyloxy)ethanamine conducted under the catalyst-free conditions (entry 4) and in the presence
of Pd(dba)2/BINAP (entry 5). The yield of the product is slightly increased (from 37% to 49%) in the
Pd-catalyzed reaction indicating that the catalytic conditions may be useful even for the amination of
the most reactive Phen halides.
Finally, the steric hindrances at the 1,10-phenanthroline N,N-chelating site introduced by two
methyl substituents at position of the pyridine ring have a positive effect on the product yield. The
amination of 4,7-dibromo-2,9-dimethylphenanthroline with 2-(1-adamantyloxy)ethanamine
(Pd(dba)2/BINAP, Cs2CO3, entry 7) gave the target product in 74% yield which is higher compared to
that observed in the amination of 4,7-dibromophenanthroline (entry 6).126
In contrast to the substitution of two halogen atoms of aryl dihalides,127 the sequential reactions
of two halogen atoms located at different pyridine rings of Phen core by amine residues affords the
product in the yields comparable to those observed in the amination of mono-halides because
electronic effects of the amino substituent do not perturb the second amination reaction (entries 68,
1012 and 14).128
In spite of the need in the adjustment of the reaction conditions to the structure of Phen halide
and amine, Pd-catalyzed amination reaction is a useful synthetic tool to prepare unusual ligands for
many practical applications. For instance, it was employed for the one-pot synthesis of a novel series
of N- and O-containing macrocyclic ligands which display an externally directed 4,7-amino-1,10-
phenanthroline moiety (Table 8). The macrocyclization of 4,7-dibromo-1,10-phenanthrolines with
linear polyoxadiamines proceeds in the presence [Pd(dba)2]/BINAP catalytic system with Cs2CO3 in
dioxane at reflux (entry 1). Linear polyamines are well-known chelators for the palladium(II) ion, what
complicates their use in Pd-catalyzed amination reactions.127 Therefore, it is not surprising that the
[Pd(dba)2]/BINAP catalytic system employed with Cs2CO3 in dioxane at reflux demonstrated very
poor efficiency in this macrocyclization reaction (entry 2). On the contrary, [Pd(dba)2]/Josiphos
afforded macrocycles in reasonable yields when the amount of cesium carbonate was increased up to
10 equivalents (entries 3 and 4). Interestingly, that more reactive 2,9-dimethyl-substituted dibromide
reacts with linear polyamines in the presence of a less expensive [Pd(dba)2]/BINAP catalyst giving the
products in similar yields (entries 7 and 8).
 18

Table 7. Buchwald-Hartwig amination of 1,10-phenanthrolines.

R R
Hal Hal R [Pd]/L N N
+ NH R' R'
N N R' base
N N

Entry Posi- Hal Amine Catalyst Reaction conditions Yield, Ref.

tion(s) (mol%) (%)
1a 5 Br n-Bu-NH2 Pd2(dba)3/BINAPb tBuONa, toluene, reflux, 1 h 54 129

(5/10)
130
2 5 Br N-Boc-piperazine Pd2(dba)3/BINAP tBuONa, toluene, reflux, 16 h 80
(5/10)
3 5 Br 2-(1-adamantyloxy) Pd(dba)2/Josiphosc tBuONa, dioxane, reflux, 24 h 63 126

ethanamine (8/9)
126
4 4 Cl 2-(1-adamantyloxy) Pd(dba)2/Josiphos K2CO3, DMF, reflux, 24 h 37
ethanamine (8/9)
126
5 4 Cl 2-(1-adamantyloxy) Pd(dba)2/BINAP Cs2CO3, dioxane, reflux, 24 h 49
ethanamine (4/4.5)
126
6 4,7 Br 2-(1-adamantyloxy) Pd(dba)2/Josiphos Cs2CO3, dioxane, reflux, 24 h 58
ethanamine (8/9)
7d 4,7 Br 2-(1-adamantyloxy) Pd(dba)2/Josiphos Cs2CO3, dioxane, reflux, 24 h 74 126

ethanamine (8/9)
131
8 4,7 Cl (4-tert-Bu-Ph)2NH Pd(OAc)2/tBu3P tBuONa, o-xylene, reflux, 8 h 47
(4/8)
126
9 3 Br 2-(1-adamantyloxy) Pd(dba)2/Josiphos tBuONa, dioxane, reflux, 24 h 60
ethanamine (8/9)
10 3,8 Br Ph2NH Pd2(dba)3/Xantphose tBuONa, toluene, 100oC, 24 h 56 132

(12/31)
11 3,8 Br carbazole Pd2(dba)3/Xantphos tBuONa, toluene, 100oC, 24 h 30 132

(12/31)
12 3,8 Br phenoxazine Pd2(dba)3/Xantphos tBuONa, toluene, 100oC, 24 h 83 132

(12/31)
13 2 Br 1,5,7-triazabicyclo- Pd(OAc)2/BINAP tBuOK, toluene, 90oC, 3 h 87 133

[4.4.0]dec-5-ene (2/3)
14 2,9 Cl 2-aminopyridine Pd2(dba)3/DPPF AcONa, toluene, 100oC, 60 h 75 128

a b
5-Bromo-2,9-dimethy-1,10-phenanthroline was used. BINAP=2,2′-bis(diphenylphosphino)-1,1′-binaphthyl.
c
Josiphos=(R)-1-[(SP)-2-(diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine. d4,7-Dibromo-2,9-dimethyl-1,10-
phenanthroline was used. eXantPhos=4,5-bis(diphenylphosphino)-9,9-dimethylxanthene.

To note, the catalyst-free nucleophilic substitution is not suitable for the preparation of these
macrocyclic ligands even with polyamines bearing protected secondary amino groups because it
demands dilution and stoichiometric amounts of the reagents.
Sensing properties of ditopic ligands thus prepared were briefly investigated after their
coordination to [Ru(II) reacting the ligands with Ru(bpy)2Cl2.126 One of these complexes exhibits a
selective dual-channel (UV-vis and fluorescence) response on the presence of Cu(II) ions in the
studied solutions.
 19

Table 8. Synthesis of macrocyclic ligands according the Pd-catalyzed amination reaction.

Entry R Product Ligand, L Cs2CO3, Yield,

(equiv.) (%)

1 H A BINAP 4 20

2 H B BINAP 10 5

3 H B Josiphos 10 35

4 H B Josiphos 4 10

5 H C Josiphos 10 17

6 H D Josiphos 10 25

7 Me E BINAP 10 33

8 Me F BINAP 10 30

CP bond forming reactions

Phosphorous containing Phens have been attracted considerable interest for a long time as
promising ligands for catalysis, ligands for separation of actinides from lanthanides and valuable
building blocks in supramolecular chemistry.134-137
The Pd-catalyzed reaction was found to be efficient to prepare phosphonates and posphine
oxides bearing the phenanthrolinyl residue at the phosphorous atom. It’s worth noting that - and -
phosphorous-containing Phens can be prepared through non-catalytic approaches, while all  and 
isomeric compounds were obtained via catalytic transformations.
The Hirao reaction138,139 was the first Pd-catalyzed CP bond forming reaction which was
successfully employed by us to introduce the diethoxyphosphoryl substituent at all carbon atoms of the
heterocyclic core (Table 9).140 The products were obtained in good yields by reacting bromides with
diethyl phosphite using palladium(II) acetate and bidentate phosphine ligand (DPPF) while classical
triphenylphosphine was inefficient in this transformation (entries 1, 2 and 3). Interestingly, readily
available - and -chlorophenanthrolines also smoothly reacted under these conditions (entries 3 and
8). Diphosphonates were prepared in good yields through the phosphonylation of dihalides (entries 4,
5, 7 and 10).
The new synthesized phosphonate derivatives are of interest for obtaining unusual polynuclear
complexes, water soluble catalytic systems and for development of stable heterogenized catalytic
systems.141-144
 20
Recently, Borisova and coworkers have shown that Pd(OAc)2/DPPF catalytic system works well
for coupling 2-chloro- and 2,9-dichloro-1,10-phenanthrolines with secondary phosphine oxides in
DMF (entries 11, 12 and 13).145 This is a promising one-step synthetic approach to hard- and soft
phosphine oxide receptors for f-element complexation that can replace classical non-catalytic synthetic
methods.136,146

Table 9. Functionalization of Phens according Pd-catalyzed C–P bond forming reactions.

Hal Hal Pd(OAc)2/DPPF RR’(O)P P(O)RR’

+ HP(O)RR’
base
N N N N

Entry Posi- Hal R R’ Catalyst, Conditions Yield, Ref.

tion(s) (mol%) (%)
136
1 5 Br OEt OEt 5/10 Et3N, toluene, reflux, 20 h 80
136
2 4 Br OEt OEt 10/20 Et3N, dioxane, reflux, 12 h 52
3 4 Cl OEt OEt 10/20 Et3N, dioxane, reflux, 12 h 55a 143

136
4 4,7 Br OEt OEt 10/20 Et3N, toluene, reflux, 20 h 71
5 4,7 Cl OEt OEt 10/20 Et3N, toluene, reflux, 20 h 69a 143

140
6 3 Br OEt OEt 5/10 Et3N, toluene, reflux, 5 h 81
140
7 3,8 Br OEt OEt 10/20 Et3N, toluene, reflux, 5 h 70
140
8 2 Cl OEt OEt 10/20 Et3N, toluene, reflux, 20 h 71
146
9 2 Cl Ph Ph 1/2 K2CO3, DMF, 120°C, 7 h 98
140
10 2,9 Cl OEt OEt 10/20 Et3N, toluene, reflux, 3 h 80
145
11 2,9 Cl Ph Ph 2/4 K2CO3, DMF, 80°C, 7 h 79
145
12 2,9 Cl Ph tBu 2/4 K2CO3, DMF, 80°C, 7 h 71
a Unpublished data.

Unsymmetrical diphosphoryl-substituted Phens were only obtained according to a stepwise

reaction of 2,9-dichloro-1,10-phenanthroline with substoichiometric amounts of phosphine oxides
(Scheme 21).148 However, the regioselectivity of the first coupling was quite low even when DPPF
was replaced by DPEPhos (DPEPhos = (Oxydi-2,1-phenylene)bis(diphenylphosphine)) ligand.

Ph2P(O)H (0.55 equiv.)

nOct2P(O)H
Pd(OAc)2/DPEPhos
(2/4 mol%) Pd(OAc)2/DPPF
(2.5/5 mol%)
N N K2CO3, DMF
N N Cs2CO3, DMF N N
Cl Cl 110°C, 7h
Cl P(O)Ph2 110°C, 20h nOct2(O)P P(O)Ph2
38% 47%

Scheme 21. Synthesis of unsymmetrical diphosphoryl-substituted Phen via the Pd-catalyzed coupling
reaction.

Miyaura–Ishiyama coupling

Borylation of halo-substituted Phens has been accomplished in high yields using Pd57 and Ir96
catalysts (Scheme 22) but boron-containing Phens are still rarely used as intermediate compounds in
the preparation of functionalized ligands. These compounds can form intermolecular complexes by
boron coordination to the nitrogen atom of the heterocycle what probably causes inconveniences for
their purification and handling.
 21

Scheme 22. Catalytic borylation of bromo-1,10-phenanthrolines.

3.3 Carboalkoxylation of Phens

The carboalkoxylation of aryl halides mediated by palladium(0) complexes was pioneered by Heck149
and applied to functionalization of reactive 2,9-dichloro-1,10-phenanthroline by Zeissel and El-
ghayoury.150 Later the experimental conditions for the ester preparation from all isomeric halogen-
substituted Phens were reported (Table 10). The reactions were commonly conducted in refluxing
alcohols in a continuous flow of carbon monoxide at atmospheric pressure with palladium(0)
complexes with triphenylphosphine or bidentate phosphine ligands such as XantPhos (entries 2–4, 6
and 7). The best choice of alcohol is determined by a solubility of the starting halide and the target
ester. Carbomethoxylation which is commonly used for the synthesis of aryl carboxylic acids was
rarely performed in Phen series probably due to a low solubility of methyl
phenanthrolinylcarboxylates. For instance, methoxycarbonylation of 3,8-dibromo-1,10-phenanthroline
in methanol in the presence of Pd(OAc)2/Xantphos afforded a mixture of 3-(methoxycarbonyl)- and
3,8-di(methoxycarbonyl)-1,10-phenanthrolines which were found to be inseparable by column
chromatography.151 In contrast, pure 3,8-di(butoxycarbonyl)-1,10-phenanthroline can be isolated in
good yield performing the ester synthesis in n-butanol.

Table 10. Carboalkoxylation of Phens.

Hal Hal CO, ROH ROOC COOR

N N [Pd]/L, base
N N

Entry Posi- Hal R Reagent Catalyst Conditions Yield, Ref.

tion(s) [Pd]/L (mol%) (%)
1 5 Br Me CO, Et3N Pd(PPh3)2Cl2 (5) MeOH, 100oC, 4 bar, 6 h 66 154

2a 4 Br Me CO, Et3N Pd(dba)2/DPPPb (5/5) MeOH, 150oC, 30 bar, 16 h 44 14

3 3 Br nBu CO, K2CO3 Pd(OAc)2/Xantphosc (4/8) nBuOH, 90oC, 1 bar, 3 h 66 151

4 3,8 Br nBu CO, K2CO3 Pd(OAc)2/Xantphos (5/10) nBuOH, 90oC, 1 bar, 3 h 70 151

5b 3,8 Br H N-formyl- Pd(OAc)2/Xantphos (6/9) DMF, 80oC, 72 h 81 152

saccharin, KF
6 2,9 Cl nBu CO, Bu3N Pd(PPh3)2Cl2 (2) nBuOH, 120oC, 1 bar, 72 h 60 150

7 2 Cl nBu CO, Bu3N Pd(PPh3)2Cl2 (2) nBuOH, 120oC, 1 bar, 72 h 62 150

9 Br
a
4-Bromo-7-methyl-1,10-phenanthroline was used. bThe target 3,8-dicarboxy-1,10 phenanthroline was obtained after
hydrolysis of intermediate compound in Et3N-water mixture (7:10 v/v %) at room temperature

Methoxycarbonylation of 4-bromo and 5-bromo-1,10-phenanthrolines was carried out in autoclave

at 100–150°C (entries 1 and 2) but comparative studies at atmospheric pressure were not reported in
both case. Farha, Delferro and coworkers152 employed N-formylsaccharin as a source of carbon
 22
monoxide (entry 5) following the earlier reported procedure for the preparation of acids from aryl
halide.153

3.4 Cyanation

Palladium-catalyzed cyanation reaction155 successfully proceeds with Phen derivatives though

the number of examples is limited (Table 11). Dibromo-substituted Phens were reacted with sodium
cyanide using the Pd(OAc)2/DPPENT catalytic system and TMEDA as a base in mesitylene at reflux
(entries 1, 2 and 5).156

Table 11. Cyanation of Phens.

Hal Hal M(CN)n NC CN

N N catalyst
N N

Entry Posi- Hal M(CN)n Catalyst Conditions Yield, Ref.

tion(s) (mol%) (%)
1 5,6 Br NaCN Pd(OAc)2/DPPENTa (5/20) TMEDA, mesitylene, 12 h, reflux 52 156

156
2 4,7 Br NaCN Pd(OAc)2/DPPENT TMEDA, mesitylene, reflux, 12 h 60
3 4 Cl Zn(CN)2 Pd(dba)2/DPPF/Zn (2/2/10) DMA, 130oC (MW), 1 h 70 157

4 4,7 Cl Zn(CN)2 Pd(dba)2/DPPF/Zn (6/6/10) DMA, 130oC (MW), 1 h 65 157

156
5 3,8 Br NaCN Pd(OAc)2/DPPENT (5 /20) mesitylene, 12 h, reflux 62
a
DPPENT = 5-bis(diphenylphosphino)pentane.

To perform the reaction with chloro-substituted Phens, the conditions developed for aryl
chlorides158 proved to be suitable (entries 3 and 4). 4-Chloro- and 4,7-dichloro-1,10-phenanthrolines
were transformed into corresponding cyanides using Zn(CN)2 as a cyanide source, Pd(dba)2/DPPF
catalytic system and a catalytic amount of zinc powder. The use of the microwave assistance in these
reactions allowed shorten the reaction time and a lower catalyst loading without diminishing the
yields.157
To note, the cyanides thus prepared are convenient intermediate compounds in the synthesis of
amides or oximes according to standard methods.

4. Functionalization of metal complexes with 1,10-phenanthroline ligands

Catalytic transformations of metal complexes with 1,10-phenanthroline ligands is a synthetic

alternative to the preparation of the complexes by the metal coordination to already modified chelators.
This synthetic strategy is useful for the preparation of thermodynamic stable and inert complexes such
as Ru(II), Ir(III), Os(II) complexes with Phen ligands. These syntheses of TM complexes allow to
avoid binding the catalyst with phenanthroline substrates and to increase the reactivity of Phens due to
electron-accepting capacity of positively charged metal ions. These benefits are balanced by the
demands of specific techniques for the purification of polar complexes which are hardly compatible
with classical column chromatography. Nevertheless, in some cases this strategy is the only possible,
especially in the synthesis of polynuclear complexes when the selective coordination of polytopic
ligands cannot be easily achieved. For instance, Pd(IIRu(II) bimetallic complexes were prepared
according to this approach (Scheme 23).159 First, the Suzuki-Miyaura reaction was employed for the
functionalization of the Ru(II) complex by the bpy residue. Then the chelator thus obtained was
coordinated to Pd(II) ions in order to obtain the bimetallic catalyst.
 23

(HO)2B 2+
2+ N
N RuII(bpy)2
N N N
RuII(bpy) 2
Br N N
Pd(PPh3)4, Et3N
DMF, 120oC 54%
N

[(COD)Pd(C3H5)]BF4
Ru(bpy)2Cl2
3+

Br N N
Pd

N N RuII(bpy)2

N N

Scheme 23. Suzuki-Miyaura reaction in the synthesis of dinuclear Pd(II)Ru(II)complex.

The reductive dimerization of the Ru(II) complex with 5-chloro-1,10-phenanthroline was

successfully carried out in the presence of Ni(0) catalyst, and the target product was isolated in a good
yield (Scheme 24).160 This method was also used for the synthesis of Ir(III) and Os(II) complexes
which were obtained in comparable yields. In contrast, attempt to perform the dimerization of metal-
free 5-chloro-1,10-phenanthroline by using the same conditions failed.

Scheme 24. Reductive coupling of ruthenium(II) complex with 5-chloro-1,10-phenanthroline.

Some other examples of coupling reactions in metal complexes with halo-substituted Phens are
summarized in Table 12. The most abundant are reactions of Ru(II) and Ir(III) complexes, in particular
the Suzuki-Miyaura and Sonogashira couplings affecting ,  and  positions of the heterocycle. For
instance, the Sonogashira coupling using the Ru(II) complex with 5-chloro-1,10-phenanthroline gave
the product in 65% yield (entry 9),47 while the analogous reaction of 5-chloro-1,10-phenanthroline
provided substantially smaller product yield.45 Rhenium(I) carbonylates are more difficult substrates
which generally afford poorer yields in similar reactions due to the ligand exchange between the
complex and the catalyst (entry 13). The Sonogashira reaction involving the Pt(II) complex with 5-
bromo-1,10-phenanthroline was also accompanied by the side ligand exchange reaction, in this case
the chloride ligand in the coordination sphere of the platinum atom was replaced by the acetylenide
ligand (entry 8).
 24

Table 12. Catalytic functionalization of 1,10-phenanthroline complexes.

Hal Hal R R
catalyst
N N
+ R Y
N N
MLn MLn

Entry Posi- Hal MLn Reaction Catalyst Yield, Ref.

tion(s) (%)
161
1 5 Br Ru(4,4’-bis(tBu)bpy)2 Suzuki-Myaura Pd(PPh3)2Cl2 97
162
2 5 Br Ru(4,4’-bis(tBu)bpy)2 Sonogashira Pd(PPh3)2Cl2/CuI 73
161
3 5,6 Br Ru(4,4’-bis(tBu)bpy)2 Suzuki-Myaura Pd(PPh3)2Cl2 68
46
4 5,6 Br Ru(4,7-bis(Ph)Phen)2 Sonogashira Pd(PPh3)2Cl2/CuI 57
163
5 5 Br Ir(ppy)2 Sonogashira Pd(PPh3)2Cl2/CuI 54
163
6 5,6 Br Ir(ppy)2 Sonogashira Pd(PPh3)2Cl2/CuI 62
164
7 5 Br Ir(ppy)2 Suzuki-Myaura Pd(OAc)2 76
8 5 Br PtCl2 a Sonogashira Pd(PPh3)2Cl2/CuI 25a 36

47
9 5 Cl Ru(bpy)2 Sonogashira Pd(PPh3)2Cl2/CuI 65
47
10 4 Cl Ru(bpy)2 Sonogashira Pd(PPh3)2Cl2/CuI 85
47
11 4,7 Cl Ru(bpy)2 Sonogashira Pd(PPh3)2Cl2/CuI 75
165
12 4 Br Ru(Phen)2 Sonogashira Pd(PPh3)2Cl2/CuI 50
166
13 4 Br Re(CO)3Br Sonogashira Pd(PPh3)2Cl2/CuI 15
167
14 4,7 Br Re(CO)3Br Sonogashira Pd(PPh3)2Cl2/CuI 69
47
15 3 Br Ru(bpy)2 Sonogashira Pd(PPh3)2Cl2/CuI 75
163
16 3 Br Ir(ppy)2 Sonogashira Pd(PPh3)2Cl2/CuI 59
168
17 3,8 Br Ir(ppy)2 Suzuki-Myaura Pd(PPh3)4 75
163
18 3,8 Br Ir(ppy)2 Sonogashira Pd(PPh3)2Cl2/CuI 63
169
19 3,8 Br Co(3,3’- Mizoroki-Heck Pd(OAc)2/P(o-Tol)3 41
bis(COOH)bpy)2(OAc)2
169
20 3,8 Br Zn(3,3’- Mizoroki-Heck Pd(OAc)2/P(o-Tol)3 45
bis(COOH)bpy)2(OAc)2
170
21 3,8 Br Ru(4,4’-bis(C10H21)bpy)Cl2 Stille coupling Pd(PPh3)4 32
171
22 2,9 Br Re(CO)3Br Suzuki-Myaura Pd(OAc)2/ 30
PPh3
a
Substitution of chlorine atom for alkyne residue in the coordination sphere of Pt was observed.

Recently, these reactions have found interesting applications in the synthesis of cross-linked
polymers. E.g. the Stille coupling employing distannyl substituted aromatic compounds and Ru(II)
complexes with 3,8-dibromo-1,10-phenanthroline afforded fluorescent polymers (entry 21).170
Analogous approach using the Mizoroki-Heck reaction provided Co(II)- and Zn(II)-containing
phenanthroline-based polymers (entry 19).169
The Pd-catalyzed coupling reactions can be carried out in several ligands coordinated to a metal
center. Thus, the Sonogashira reaction allows to prepare the hexasubstituted Ru(II) complex
containing three di(ethynyl)phenanthroline ligands by the substitution of six bromine atoms in the
starting complex (Scheme 25).172
 25
R R

2+ 2+
Br Br

N N N N
H R
R N N R R= B
Br N RuII N Br RuII
Pd(PPh3)2Cl2, CuI
N N Et3N, CH3CN N N

Br Br

R R
42%

Scheme 25. Introduction of six ethynyl substituents in the Ru(II) complex with 4,7-dibromo-1,10-
phenanthroline via the Sonogashira reaction.

Catalytic reactions were also used in the synthesis of chiral complexes. For instance, it was
found possible to resolve Δ and Λ isomers of Ru(II) complex bearing 3-bromo-1,10-phenanthroline
and 2,2’-bipyridine ligands. Kinetical inertness of these complexes allows for their chemical
transformations with the retention of configuration. Using the Sonogashira coupling, Tzalis and Tor
managed to synthesize all possible stereoisomers (ΔΛ, ΔΔ and ΛΛ) of binuclear complexes and
studied their photophysical properties (Scheme 26).173

Scheme 26. Synthesis of chiral dinuclear ruthenium(II) complexes via the Sonogashira coupling.

5. Conclusion

Phen is a classical ligand in coordination chemistry which is renowned among bidentate nitrogen
ligands for the exceptional properties of its stable metal complexes. Rapid development of synthetic
approaches to Phen derivatives has been promoted by the increase of the interest in their complexes in
many fundamental and practical applications. During last three decades TM-catalyzed cross-coupling
reactions have become a powerful tool for the synthesis of Phen ligands. They allow for the
preparation of 3- and 5-substituted derivatives which are hardly available through other synthetic
approaches. Moreover, they are expanded beyond the scope of the nucleophilic substitution reaction
for other isomeric halo-substituted phenanthrolines. Among different TM catalysts, palladium
complexes seem to be the most efficient for the functionalization of these bidentate chelators. The
Suzuki-Miyaura and Sonogashira reactions allow for the CC bond formation at all positions of the
heteroaromatic scaffold in the presence of available and simple catalytic systems. However, in many
other cases the catalytic processes are hindered by the coordination properties of these bidentate
ligands, thus demanding a fine adjustment of the catalytic systems. In some cases, the application of
1,10-phenanthroline metal complexes as substrates in TM-catalyzed reactions is also possible provided
 26
the complexes possess enough high kinetic and thermodynamic stability to prevent their degradation in
the course of catalytic transformations. Comparing catalytic chemistry of Phens with that of other
aromatic derivatives, it’s worth noting that many synthetic methods such as C–Het (Het = O, S)
coupling, direct CH functionalization, selective C(sp3)–C(sp2) bond formation are still
underdeveloped for these compounds. Thus, we expect that the merge of the catalytic chemistry with
Phen chelators will bring forward not only novel amazing reactions in which Phens serve as ligands
but also useful synthetic approaches for the preparation of these ligands.

Acknowledgement

This work was supported by the Russian Foundation for Basic Research (grant N 18-29-04030) and
the Centre National de la Recherche Scientifique (CNRS). It was accomplished in the frame of the
collaborative agreement between ENS de Lyon and Lomonosov Moscow State University (2012-
2021). A. Abel is grateful to the French government and French embassy in Russia for Mechnikov
2019 Grant.

References

1. Ziessel, R. Coord. Chem. Rev. 2001, 216−217, 195−223.

2. Schubert, U. S.; Eschbaumer, C. Angew. Chem., Int. Ed. 2002, 41, 2892−2926.
3. Accorsi, G.; Listorti, A.; Yoosaf, K.; Armaroli, N. Chem. Soc. Rev. 2009, 38, 1690−1700.
4. Saha, M. L.; Neogi, S.; Schmittel, M. Dalton Trans. 2014, 43, 3815−3834.
5. Niess, F.; Duplan, V.; Diercks, C. S.; Sauvage, J.-P. Chem. − Eur. J. 2015, 21, 14393−14400.
6. Sammes, P. G.; Yahioglu, G. Chem. Soc. Rev. 1994, 23, 327−334.
7. Bencini, A.; Lippolis, V. Coord. Chem. Rev. 2010, 254, 2096−2180.
8. Bonacorso, H. G.; Andrighetto, R.; Frizzo, C. P.; Zanatta, N.; Martins, M. A. P. Targets
Heterocycl. Syst. 2015, 19, 1−27.
9. Piepenbrock, M.-O. M.; Lloyd, G. O.; Clarke, N.; Steed, J. W. Chem. Rev. 2010, 110,
1960−2004.
10. Zhao, Q.; Li, F.; Huang, C. Chem. Soc. Rev. 2010, 39, 3007−3030.
11. Butler, S. J.; Parker, D. Chem. Soc. Rev. 2013, 42, 1652−1666.
12. Heinemann, F.; Karges, J.; Gasser, G. Acc. Chem. Res. 2017, 50, 2727−2736.
13. Durand, J.; Milani, B. Coord. Chem. Rev. 2006, 250, 542−560.
14. Ferretti, F.; Ragaini, F.; Lariccia, R.; Gallo, E.; Cenini, S. Organometallics 2010, 29,
1465−1471.
15. Wang, D.; Weinstein, A. B.; White, P. B.; Stahl, S. S. Chem. Rev. 2018, 118, 2636−2679.
16. Dou, S.; Song, J.; Xi, S.; Du, Y.; Wang, J.; Huang, Z.-F.; Xu, Z. J.; Wang, X. Angew. Chem., Int.
Ed. 2019, 58, 4041−4045.
17. Wu, F.; Xie, J.; Zhu, Z. Appl. Organomet. Chem. 2020, 34, e5926.
18. Reiser, O. Acc. Chem. Res. 2016, 49, 1990−1996.
19. Levi, N.; Amir, D.; Gershonov, E.; Zafrani, Y. Synthesis 2019, 51, 4549−4567.
20. Qin, Y.; Chen, L.; Chen, G.; Guo, Z.; Wang, L.; Fan, H.; Robert, M.; Lau, T.-C. Chem.
Commun. 2020, 56, 6249−6252.
21. Hagfeldt, A.; Boschloo, G.; Sun, L.; Kloo, L.; Pettersson, H. Chem. Rev. 2010, 110, 6595−6663.
22. Luman, C. R.; Castellano, F. N. In Comprehensive Coordination Chemistry, McCleverty, J. A.;
Meyer, T. J.; Lever, A. B. P., Eds., Elsevier: Oxford, 2004, Vol. 1, p 25−39.
23. Halcrow, B. E.; Kermack, W. O. J. Chem. Soc. 1946, 155−157.
24. Yamada, M.; Nakamura, Y.; Kuroda, S.; Shimao, I. Bull. Chem. Soc. Jpn. 1990, 63, 2710−2712.
25. Guo, H. C.; Zheng, R. H.; Jiang, H. J. Org. Prep. Proced. Int. 2012, 44, 392−396.
26. Toyota, S.; Woods, C. R.; Benaglia, M.; Siegel, J. S. Tetrahedron Lett. 1998, 39, 2697−2700.
27. Tzalis, D.; Tor, Y.; Salvatorre, F.; Jay Siegel, S. Tetrahedron Lett. 1995, 36, 3489−3490.
28. Saitoh, Y.; Koizumi, T.-A.; Osakada, K.; Yamamoto, T. Can. J. Chem. 1997, 75, 1336−1339.
29. Dietrich-Buchecker, C.; Jiménez, M. C.; Sauvage, J.-P. Tetrahedron Lett. 1999, 40, 3395−3396.
 27
30. Výprachtický, D.; Kaňková, D.; Pokorná, V.; Kmínek, I.; Dzhabarov, V.; Cimrová, V. Aust. J.
Chem. 2014, 67, 915−921.
31. Sharma, K. K.; Patel, D. I.; Jain, R. Chem. Commun. 2015, 51, 15129−15132.
32. Wang, L.; Monro, S.; Cui, P.; Yin, H.; Liu, B.; Cameron, C. G.; Xu, W.; Hetu, M.; Fuller, A.;
Kilina, S.; McFarland, S. A.; Sun, W. ACS Appl. Mater. Interfaces 2019, 11, 3629−3644.
33. Klosterman, J. K.; Linden, A.; Siegel, J. S. Org. Biomol. Chem. 2008, 6, 2755−2764.
34. Graf, G. I.; Hastreiter, D.; da Silva, L. E.; Rebelo, R. A.; Montalban, A. G.;McKillop, A.
Tetrahedron 2002, 58, 9095−9100.
35. Mlochowski, J. Rocz. Chem. 1974, 48, 2145−2155.
36. Hissler, M.; Connick, W. B.; Geiger, D. K.; McGarrah, J. E.; Lipa, D.; Lachicotte, R. J.;
Eisenberg, R. Inorg. Chem. 2000, 39, 447−457.
37. Monro, S.; Scott, J.; Chouai, A.; Lincoln, R.; Zong, R.; Thummel, R. P.; McFarland, S. A. Inorg.
Chem. 2010, 49, 2889−2900.
38. Klosterman, J. K.; Linden, A.; Siegel, J. S. Org. Biomol. Chem. 2008, 6, 2755−2764.
39. Sun, W.-W.; Liu, J.-K.; Wu, B. Org. Chem. Front. 2019, 6, 544−550.
40. Suffert, J.; Ziessel, R. Tetrahedron Lett. 1991, 32, 757−760.
41. Ziessel, R.; Suffert, J.; Youinou, M.-T. J. Org. Chem. 1996, 61, 6535-6546.
42. Trolez, Y.; Finke, A. D.; Silvestri, F.; Monti, F.; Ventura, B.; Boudon, C.; Gisselbrecht, J.-P.;
Schweizer, W. B.; Sauvage, J.-P.; Armaroli, N.; Diederich, F. Chem. − Eur. J. 2018, 24,
10422−10433.
43. Passays, J.; Rubay, C.; Marcélis, L.; Elias, B. Eur. J. Inorg. Chem. 2017, 623−629.
44. Lincoln, R.; Kohler, L.; Monro, S.; Yin, H.; Stephenson, M.; Zong, R.; Chouai, A.; Dorsey, C.;
Hennigar, R.; Thummel, R. P.; McFarland, S. A. J. Am. Chem. Soc. 2013, 135, 17161−17175.
45. Miller, M. T.; Karpishin, T. B. Inorg. Chem. 1999, 38, 5246−5249.
46. Goze, C.; Sabatini, C.; Barbieri, A.; Barigelletti, F.; Ziessel, R. Eur. J. Inorg. Chem. 2008,
1293−1299.
47. Glazer, E. C.; Magde, D.; Tor, Y. J. Am. Chem. Soc. 2007, 129, 8544−8551.
48. Manca, P.; Gladiali, S.; Cozzula, D.; Zucca, A.; Sanna, G.; Spano, N.; Pilo, M. I. Polymer 2015,
56, 123−130.
49. Schmittel, M.; Ganz, A. Synlett 1997, 710-712.
50. Michel, C.; Habibi, D.; Schmittel, M. Molecules 2001, 6, M226.
51. Schmittel, M.; Michel, C.; Wiegrefe, A. Synthesis 2005, 367−373.
52. Yang, J.; Dass, A.; Sotiriou-Leventis, C.; Tyson, D. S.; Leventis, N. Inorg. Chim. Acta 2005,
358, 389−395.
53. Vrabel, M.; Hocek, M.; Havran, L.; Fojta, M.; Votruba, I.; Klepetarova, B.; Pohl, R.; Rulisek, L.;
Zendlova, L.; Hobza, P.; Shih, I. H.; Mabery, E.; Mackman, R. Eur. J. Inorg. Chem. 2007,
1752−1769.
54. Sjoegren, M.; Hansson, S.; Norrby, P. O.; Aakermark, B.; Cucciolito, M. E.; Vitagliano, A.
Organometallics 1992, 11, 3954−3964.
55. Gavette, J. V.; Evoniuk, C. J.; Zakharov, L. N.; Carnes, M. E.; Haley, M. M.; Johnson, D. W.
Chem. Sci. 2014, 5, 2899−2905.
56. Lam, F.; Chan, K. S.; Liu, B.-J. Tetrahedron Lett. 1995, 36, 6261−6262.
57. Hossain, M. D.; Zhang, J.; Pandey, R. K.; Sato, T.; Higuchi, M. Eur. J. Inorg. Chem. 2014,
3763−3770.
58. Dietrick-Buchecker, C. O.; Marnot, P. A.; Sauvage, J. P. Tetrahedron Lett. 1982, 23,
5291−5294.
59. Mörtel, M.; Lindner, T.; Scheurer, A.; Heinemann, F. W.; Khusniyarov, M. M. Inorg. Chem.
2020, 59, 2659−2666.
60. Tyson, D. S.; Henbest, K. B.; Bialecki, J.; Castellano, F. N. J. Phys. Chem. A 2001, 105,
8154−8161.
61. Shillito, G. E.; Hall, T. B. J.; Preston, D.; Traber, P.; Wu, L.; Reynolds, K. E. A.; Horvath, R.;
Sun, X. Z.; Lucas, N. T.; Crowley, J. D.; George, M. W.; Kupfer, S.; Gordon, K. C. J. Am.
Chem. Soc. 2018, 140, 4534−4542.
62. Nair, N. V.; Zhou, R.; Thummel, R. P. Inorg. Chim. Acta 2017, 454, 27−39.
 28
63. Ko, C.-C.; Kwok, W.-M.; Yam, V. W.-W.; Phillips, D. L. Chem. − Eur. J. 2006, 12,
5840−5848.
64. Schaefer, B.; Goerls, H.; Meyer, S.; Henry, W.; Vos, J. G.; Rau, S. Eur. J. Inorg. Chem. 2007,
4056−4063.
65. Edwards, A. C.; Geist, A.; Mullich, U.; Sharrad, C. A.; Pritchard, R. G.; Whitehead, R. C.;
Harwood, L. M. Chem. Commun. 2017, 53, 8160−8163.
66. Edwards, A. C.; Wagner, C.; Geist, A.; Burton, N. A.; Sharrad, C. A.; Adams, R. W.; Pritchard,
R. G.; Panak, P. J.; Whitehead, R. C.; Harwood, L. M. Dalton Trans. 2016, 45, 18102−18112.
67. Li, C.; Schwab, M.; Zhao, Y.; Chen, L.; Bruder, I.; Münster, I.; Erk, P.; Müllen, K. Dyes Pigm.
2013, 97, 258−261.
68. Wang, L.; Monro, S.; Cui, P.; Yin, H.; Liu, B.; Cameron, C. G.; Xu, W.; Hetu, M.; Fuller, A.;
Kilina, S.; McFarland, S. A.; Sun, W. ACS Appl. Mater. Interfaces 2019, 11, 3629−3644.
69. Bonnet, S.; Collin, J.-P.; Sauvage, J.-P. Inorg. Chem. 2007, 46, 10520−10533.
70. Zhang, P.; Liu, P.; Zhao, Y.; Cao, D. J. Mol. Struct. 2013, 1037, 122−129.
71. Nishikawa, Y.; Yamamoto, H. J. Am. Chem. Soc. 2011, 133, 8432−8435.
72. Peng, Y.-X.; Xu, D.; Wang, N.; Tao, T.; Hu, B.; Huang, W. Tetrahedron 2016, 72,
3443−3453.
73. Guillon, J.; Cohen, A.; Das, R. N.; Boudot, C.; Gueddouda, N. M.; Moreau, S.; Ronga, L.;
Savrimoutou, S.; Basmaciyan, L.; Tisnerat, C.; Mestanier, S.; Rubio, S.; Amaziane, S.;
Dassonville-Klimpt, A.; Azas, N.; Courtioux, B.; Mergny, J.-L.; Mullie, C.; Sonnet, P. Chem.
Biol. Drug Des. 2018, 91, 974−995.
74. Mitrofanov, A.; Brandes, S.; Herbst, F.; Rigolet, S.; Bessmertnykh-Lemeune, A.; Beletskaya, I.
J. Mater. Chem. A 2017, 5, 12216−12235.
75. Hu, M.-Y.; He, Q.; Fan, S.-J.; Wang, Z.-C.; Liu, L.-Y.; Mu, Y.-J.; Peng, Q.; Zhu, S.-F. Nat.
Commun. 2018, 9, 1−11.
76. Beyler, M.; Heitz, V.; Sauvage, J.-P. J. Am. Chem. Soc. 2010, 132, 4409−4417.
77. Luning, U.; Abbass, M.; Fahrenkrug, F. Eur. J. Org. Chem. 2002, 3294−3303.
78. Quernheim, M.; Liang, H.; Su, Q.; Baumgarten, M.; Koshino, N.; Higashimura, H.; Muellen, K.
Chem. − Eur. J. 2014, 20, 14178−14183.
79. Tao, T.; Fang, H.; Peng, Y.-X.; Zhang, M.-D.; Huang, W. Inorg. Chem. Commun. 2017, 84,
15−19.
80. Nath, M.; Roy, P.; Mishra, R.; Thakur, M. Appl. Organomet. Chem. 2019, 33, e4663.
81. Sirajuddin, M.; Ali, S.; McKee, V.; Wadood, A.; Ghufran, M. J. Mol. Struct. 2019, 1181,
93−108.
82. Zong, R.; Thummel, R. P. Inorg. Chem. 2005, 44, 5984−5986.
83. Yamada, Y.; Gohda, S.; Abe, K.; Togo, T.; Shimano, N.; Sasaki, T.; Tanaka, H.; Ono, H.; Ohba,
T.; Kubo, S.; Ohkubo, T.; Sato, S. Carbon 2017, 122, 694−701.
84. Brueckmann, J.; Heidecker, A. A.; Popovic, D.; Mengele, A. K.; Nauroozi, D.; Baeuerle, P.;
Rau, S. Eur. J. Inorg. Chem. 2019, 1832−1838.
85. Deng, S.; Krueger, G.; Taranekar, P.; Sriwichai, S.; Zong, R.; Thummel, R. P.; Advincula, R. C.
Chem. Mater. 2011, 23, 3302−3311.
86. Chen, C.-Y.; Lu, H.-C.; Wu, C.-G.; Chen, J.-G.; Ho, K.-C. Adv. Funct. Mater. 2007, 17, 29−36.
87. Chen, X.-Y.; Yang, X.; Holliday, B. J. J. Am. Chem. Soc. 2008, 130, 1546−1547.
88. Paul, B.; Chakrabarti, K.; Shee, S.; Maji, M.; Mishra, A.; Kundu, S. RSC Advances 2016, 6,
100532−100545.
89. Stones, M. K.; Banz Chung, E. M. J.; da Cunha, I. T.; Sullivan, R. J.; Soltanipanah, P.; Magee,
M.; Umphrey, G. J.; Moore, C. M.; Sutton, A. D.; Schlaf, M. ACS Catalysis 2020, 10,
2667−2683.
90. Rau, S.; Lamm, K.; Goerls, H.; Schoeffel, J.; Walther, D. J. Organomet. Chem. 2004, 689,
3582−3592.
91. Loren, J. C.; Siegel, J. S. Angew. Chem., Int. Ed. 2001, 40, 754−757.
92. Liu, Y.; Wang, Y.; Li, C.; Huang, Y.; Dang, D.; Zhu, M.; Zhu, W.; Cao, Y. Mater. Chem. Phys.
2014, 143, 1265−1270.
 29
93. Uchiyama, N.; Shirakawa, E.; Nishikawa, R.; Hayashi, T. Chem. Commun. 2011, 47,
11671−11673.
94. Larsen, M. A.; Cho, S. H.; Hartwig, J. J. Am. Chem. Soc. 2016, 138, 762−765.
95. Kieffer, J.; Divisia-Blohorn, B.; Bidan, G.; Schaffner-Hamann, C.; Kern, J.-M.; Sauvage, J.-P.
C. R. Chim. 2007, 10, 1234−1242.
96. Larsen, M. A.; Oeschger, R. J.; Hartwig, J. F. ACS Catal. 2020, 10, 3415−3424.
97. Goetz, G.; Zhu, X.; Mishra, A.; Segura, J.-L.; Mena-Osteritz, E.; Baeuerle, P. Chem. − Eur. J.
2015, 21, 7193−7210.
98. Hamilton, C. W.; Laitar, D. S.; Sadighi, J. P. Chem. Commun. 2004, 1628−1629.
99. Huang, W.; Wang, L.; Tanaka, H.; Ogawa, T. Eur. J. Inorg. Chem. 2009, 1321−1330.
100. Hu, B.; Fu, S.-J.; Xu, F.; Tao, T.; Zhu, H.-Y.; Cao, K.-S.; Huang, W.; You, X.-Z. J. Org. Chem.
2011, 76, 4444−4456.
101. Zhang, B.; Cao, K.-S.; Xu, Z.-A.; Yang, Z.-Q.; Chen, H.-W.; Huang, W.; Yin, G.; You, X.-Z.
Eur. J. Inorg. Chem. 2012, 3844−3851.
102. Huang, W.; Masuda, G.; Maeda, S.; Tanaka, H.; Hino, T.; Ogawa, T. Inorg. Chem. 2008, 47,
468−480.
103. Adeloye, A. O.; Ajibade, P. A. Int. J. Mol. Sci. 2010, 11, 3158−3176.
104. Adeloye, A. O. Molecules 2011, 16, 8353−8367.
105. Tak, J.; Kim, M.; Park, S.; Yun, S. H.; Kim, J.; Park, B.; Kim, B. H. Monatsh. Chem. 2014, 145,
1101−1108.
106. Case, F. H. J. Heterocycl. Chem. 1964, 1, 112−112.
107. Rice, C. R.; Anderson, K. M. Polyhedron 2000, 19, 495−498.
108. Iyoda, M.; Otsuka, H.; Sato, K.; Nisato, N.; Oda, M. Bull. Chem. Soc. Jpn. 1990, 63, 80−87.
109. Toyota, S.; Goto, A.; Kaneko, K.; Umetani, T. Heterocycles 2005, 65, 551−562.
110. Yang, W.; Nakano, T. Chem. Commun. 2015, 51, 17269−17272.
111. Hu, Y.-Z.; Xiang, Q.; Thummel, R. P. Inorg. Chem. 2002, 41, 3423−3428.
112. Toyota, S.; Woods, C. R.; Benaglia, M.; Haldimann, R.; Wärnmark, K.; Hardcastle, K.; Siegel, J.
S. Angew. Chem., Int. Ed. 2001, 40, 751−754.
113. Yamamoto, T.; Maruyama, T.; Zhou, Z.-H.; Ito, T.; Fukuda, T.; Yoneda, Y.; Begum, F.; Ikeda,
T.; Sasaki, S. J. Am. Chem. Soc. 1994, 116, 4832−4845.
114. Hossain, M. D.; Higuchi, M. Synthesis 2013, 45, 753−758.
115. Beletskaya, I. P.; Cheprakov, A. V. Coord. Chem. Rev. 2004, 248, 2337−2364.
116. Monnier, F.; Taillefer, M. Angew. Chem., Int. Ed. 2009, 48, 6954−6971.
117. Surry, D. S.; Buchwald, S. L. Chem. Sci. 2010, 1, 13−31.
118. Guo, L.; Deng, J.; Zhang, L.; Xiu, Q.; Wen, G.; Zhong, C. Dyes Pigm. 2012, 92, 1062−1068.
119. Wang, L.; You, W.; Huang, W.; Wang, C.; You, X.-Z. Inorg. Chem. 2009, 48, 4295−4305.
120. Jash, U.; Chakraborty, G.; Sinha, S.; Sikari, R.; Mondal, R.; Paul, N. D. Asian J. Org. Chem.
2018, 7, 1681−1688.
121. Liu, B.; Chen, C.; Zhang, Y.; Liu, X.; Chen, W. Organometallics 2013, 32, 5451−5460.
122. Hartwig, J. F. Acc. Chem. Res. 1998, 31, 852−860.
123. Wolfe, J. P.; Wagaw, S.; Marcoux, J.-F.; Buchwald, S. L. Acc. Chem. Res. 1998, 31, 805−818.
124. Wagaw, S.; Buchwald, S. L. J. Org. Chem. 1996, 61, 7240−7241.
125. Shen, Q.; Shekhar, S.; Stambuli, J. P.; Hartwig, J. F. Angew. Chem., Int. Ed. 2005, 44,
1371−1375.
126. Abel, A. S.; Zenkov, I. S.; Averin, A. D.; Cheprakov, A. V.; Bessmertnykh-Lemeune, A. G.;
Orlinson, B. S.; Beletskaya, I. P. ChemPlusChem 2019, 84, 498−503.
127. Beletskaya, I. P.; Bessmertnykh, A. G.; Averin, A. D.; Denat, F.; Guilard, R. Eur. J. Org.
Chem. 2005, 281−305.
128. Otani, T.; Tsuyuki, A.; Iwachi, T.; Someya, S.; Tateno, K.; Kawai, H.; Saito, T.; Kanyiva, K. S.;
Shibata, T. Angew. Chem., Int. Ed. 2017, 56, 3906−3910.
129. Eggert, J. P. W.; Lüning, U.; Näther, C. Eur. J. Org. Chem. 2005, 1107−1112.
130. Ghattas, W.; Cotchico-Alonso, L.; Maréchal, J.-D.; Urvoas, A.; Rousseau, M.; Mahy, J.-P.;
Ricoux, R. ChemBioChem 2016, 17, 433−440.
 30
131. Maron, A. M.; Szlapa-Kula, A.; Matussek, M.; Kruszynski, R.; Siwy, M.; Janeczek, H.; Grzelak,
J.; Mackowski, S.; Schab-Balcerzak, E.; Machura, B. Dalton Trans. 2020, 49, 4441−4453.
132. Suzuki, H.; Kanbara, T.; Yamamoto, T. Inorg. Chim. Acta 2004, 357, 4335−4340.
133. Laramee-Milette, B.; Hanan, G. S. Dalton Trans. 2016, 45, 12507−12517.
134. Ziessel, R. Tetrahedron Lett. 1989, 30, 463−466.
135. Catalano, V. J.; Bennett, B. L.; Kar, H. M.; Noll, B. C. J. Am. Chem. Soc. 1999, 121,
10235−10236.
136. Borisova, N. E.; Kharcheva, A. V.; Patsaeva, S. V.; Korotkov, L. A.; Bakaev, S.; Reshetova, M.
D.; Lyssenko, K. A.; Belova, E. V.; Myasoedov, B. F. Dalton Trans. 2017, 46, 2238−2248.
137. Xu, L.; Pu, N.; Li, Y.; Wei, P.; Sun, T.; Xiao, C.; Chen, J.; Xu, C. Inorg. Chem. 2019, 58,
4420−4430.
138. Hirao, T.; Masunaga, T.; Ohshiro, Y.; Agawa, T. Synthesis 1981, 56−57.
139. Hirao, T.; Masunaga, T.; Yamada, N.; Ohshiro, Y.; Agawa, T. Bull. Chem. Soc. Jpn. 1982, 55,
909−913.
140. Mitrofanov, A.; Lemeune, A. B.; Stern, C.; Guilard, R.; Gulyukina, N.; Beletskaya, I. Synthesis
2012, 44, 3805−3810.
141. Mitrofanov, A.; Manowong, M.; Rousselin, Y.; Brandès, S.; Guilard, R.; Bessmertnykh-
Lemeune, A.; Chen, P.; Kadish, K. M.; Goulioukina, N.; Beletskaya, I. Eur. J. Inorg. Chem.
2014, 3370−3386.
142. Mitrofanov, A. Y.; Bessmertnykh-Lemeune, A. G.; Beletskaya, I. P. Inorg. Chim. Acta 2015,
431, 297−301.
143. Mitrofanov, A.; Brandès, S.; Herbst, F.; Rigolet, S.; Bessmertnykh-Lemeune, A.; Beletskaya, I.
J. Mater. Chem. A 2017, 5, 12216−12235.
144. Mitrofanov, A. Y.; Beletskaya, I. P. Mendeleev Commun. 2019, 29, 378−379.
145. Zakirova, G. G.; Mladentsev, D. Y.; Borisova, N. E. Tetrahedron Lett. 2017, 58, 3415−3417.
146. Zakirova, G. G.; Mladentsev, D. Y.; Borisova, N. E. Synthesis 2019, 51, 2379−2386.
147. Lemeune, A.; Mitrofanov, A. Y.; Rousselin, Y.; Stern, C.; Guilard, R.; Enakieva, Y. Y.;
Gorbunova, Y. G.; Nefedov, S. E. Phosphorus, Sulfur Silicon Relat. Elem. 2015, 190, 831−836.
148. Zakirova, G. G.; Mladentsev, D. Y.; Borisova, N. N. Synlett 2020, 31, 1833−1837.
149. Schoenberg, A.; Bartoletti, I.; Heck, R. F. J. Org. Chem. 1974, 39, 3318−3326.
150. El-ghayoury, A.; Ziessel, R. J. Org. Chem. 2000, 65, 7757−7763.
151. Abel, A. S.; Mitrofanov, A. Y.; Yakushev, A. A.; Zenkov, I. S.; Morozkov, G. V.; Averin, A. D.;
Beletskaya, I. P.; Michalak, J.; Brandès, S.; Bessmertnykh-Lemeune, A. Asian J. Org. Chem.
2019, 8, 2128−2142.
152. Zhang, X.; Huang, Z.; Ferrandon, M.; Yang, D.; Robison, L.; Li, P.; Wang, T. C.; Delferro, M.;
Farha, O. K. Nat. Catal. 2018, 1, 356−362.
153. Ueda, T.; Konishi, H.; Manabe, K. Angew. Chem., Int. Ed. 2013, 52, 8611−8615.
154. Krippner, G. Y.; Harding, M. M. Tetrahedron: Asymmetry 1994, 5, 1793−1804.
155. Ellis, G. P.; Romney-Alexander, T. M. Chem. Rev. 1987, 87, 779−794.
156. Duong, A.; Maris, T.; Lebel, O.; Wuest, J. D. J. Org. Chem. 2011, 76, 1333−1341.
157. Staehle, R.; Menzel, R.; Peuntinger, K.; Pilz, T. D.; Heinemann, F. W.; Guldi, D. M.; Beckert,
R.; Rau, S. Polyhedron 2014, 73, 30−36.
158. Jin, F.; Confalone, P. N. Tetrahedron Lett. 2000, 41, 3271-3273.
159. Inagaki, A.; Nakagawa, H.; Akita, M.; Inoue, K.; Sakai, M.; Fujii, M. Dalton Trans. 2008,
6709−6723.
160. Griffiths, P. M.; Loiseau, F.; Puntoriero, F.; Serroni, S.; Campagna, S. Chem. Commun. 2000,
2297−2298.
161. Stumper, A.; Pilz, T. D.; Schaub, M.; Goerls, H.; Sorsche, D.; Peuntinger, K.; Guldi, D.; Rau, S.
Eur. J. Inorg. Chem. 2017, 3799−3810.
162. Wintergerst, P.; Mengele, A. K.; Nauroozi, D.; Tschierlei, S.; Rau, S. Eur. J. Inorg. Chem. 2019,
1988−1992.
163. Lu, Y.; Wang, J.; McGoldrick, N.; Cui, X.; Zhao, J.; Caverly, C.; Twamley, B.; O'Maille, G. M.;
Irwin, B.; Conway-Kenny, R.; Draper, S. M. Angew. Chem., Int. Ed. 2016, 55, 14688−14692.
 31
164. Kataoka, Y.; Okuno, K.; Yano, N.; Ueda, H.; Kawamoto, T.; Handa, M. J. Photochem.
Photobiol., A 2018, 358, 345−355.
165. Sakuda, E.; Ando, Y.; Ito, A.; Kitamura, N. Inorg. Chem. 2011, 50, 1603−1613.
166. Ito, A.; Kang, Y.; Saito, S.; Sakuda, E.; Kitamura, N. Inorg. Chem. 2012, 51, 7722−7732.
167. Kang, Y.; Ito, A.; Sakuda, E.; Kitamura, N. Bull. Chem. Soc. Jpn. 2017, 90, 574−585.
168. Xue, F.; Lu, Y.; Zhou, Z.; Shi, M.; Yan, Y.; Yang, H.; Yang, S. Organometallics 2015, 34,
73−77.
169. Yu, X.; Jin, X.; Tang, G.; Zhou, J.; Zhang, W.; Peng, D.; Hu, J.; Zhong, C. Eur. J. Org. Chem.
2013, 5893−5901.
170. Cheung, W. K.; Mak, C. S. K.; Chan, W. K. Macromol. Rapid Commun. 2012, 33, 585−591.
171. Wei, Q.; Dai, Y.; Chen, C.; Shi, L.; Si, Z.; Wan, Y.; Zuo, Q.; Han, D.; Duan, Q. J. Mol. Struct.
2018, 1171, 786−792.
172. Nakagawa, A.; Ito, A.; Sakuda, E.; Fujii, S.; Kitamura, N. Eur. J. Inorg. Chem. 2017, 3794-
3798.
173. Tzalis, D.; Tor, Y. J. Am. Chem. Soc. 1997, 119, 852−853.