No.

174

Science "Special" Seminar

New Ruthenium(II) Thiolate Complexes: Cooperative Activation of

E–H Bonds (E = H, Si, B) and Catalytic Applications

Martin Oestreich

Institut für Chemie, Technische Universität Berlin

Introduction bridged complexes. The polar Ru–S bond of these complexes

combines Lewis acidity at the metal center and Lewis basicity
Ruthenium(II) thiolate complexes of type [(DmpS) at the adjacent sulfur atom. This structural motif allows for
RuCl(PR3)] (1a: R = i-Pr; 1b: R = p-FC6H4), introduced by reversible heterolytic splitting of E–H bonds (E = H, Si, and B)
Ohki, Tatsumi, and Oestreich, serve as air-stable precursors across the polar Ru–S bond, generating a metal hydride and a
for cationic ruthenium(II) thiolate complexes 2 (Scheme sulfur-stabilized E+ cation (Scheme 1, bottom).[3] After transfer
1, top). These (formally) 16-valence-electron complexes of the electrophile to a Lewis-basic substrate, the resulting
are highly active bifunctional catalysts for the cooperative neutral ruthenium(II) hydride can either act as a hydride donor
activation of H–H,[1,2] Si–H[3–12] as well as B–H[13] bonds. For (reductant) or as a proton acceptor (Brønsted base), thereby
catalytic applications, the air-sensitive catalysts 2 can either be releasing dihydrogen. On the basis of this approach, complexes
preformed or generated in situ by treatment of the corresponding 2 emerged as broadly applicable catalysts for chemoselective
ruthenium(II) chloride complex 1 with NaBAr F 4 (Ar F = reductions (hydrogenation and transfer hydrogenation, [1,2]
3,5-bis(trifluoromethyl)phenyl). The tethered coordination as well as hydrosilylation[10,11]), dehydrogenative couplings
mode of the bulky 2,6-dimesitylphenyl thiolate (DmpS) ligand (Si–C(sp2),[4–6] Si–O,[7] Si–N,[8,9] and B–C(sp2)[13]), as well as
is crucial, stabilizing the coordinatively unsaturated ruthenium hydrodefluorination reactions.[12]
atom in 2 and also preventing formation of binuclear sulfur-

NaBArF4–
Ru Ru
R3P S – NaCl R3P S
Cl
BArF4–

1a: R3P = iPr3P [C3327] 2a: R3P = iPr3P

1b: R3P = (4-FC6H4)3P [C3328] 2b: R3P = (4-FC6H4)3P

+ +
H E = H H
[Ru] [Ru]
R3P SAr R3 P SAr H SiR'3
+ H H BR'2
H E E
= H and E + source
–

(catalytically active)

Scheme 1. Preparation of catalytically active ruthenium(II) thiolate complexes for cooperative E–H bond activation (E = H, Si, and B)

23
 No.174

Scope
1 - Hydrogenation and transfer hydrogenation of imines:[2]

+ BArF –
4
H–H [Ru]
Et3P SAr H R3
R3 (5 bar) N
N (3.0 mol %)
+ or
toluene or benzene R1 R2
R1 R2 H H H
0 °C or RT
aldimines, ketimines, MeO OMe
acridine, quinaldine

H H
(1.3 equiv)

2 - Regioselective electrophilic C–H silylation of indoles:[4]

+
BArF4–
H [Ru] SiMe2Ph
R2 Et3P SAr R2
(1.0 mol %)
+ Me2PhSi–H
N R1 neat N R1
PG RT–90 °C PG
PG = Me, Et, Bn, iPr3Si (1.0 equiv) – H–H ↑ C3:C2 > 99:1
R1, R2 = alkyl, aryl, F, Cl, Br

3 – Regioselective electrophilic C–H silylation of pyridines:[5]

+
BArF4–
[Ru]
R 1 iPr3P SAr R1
H (4.0 mol %) SiMe2Ph
+ Me2PhSi–H
neat
N 80 °C N

R1 = alkyl, aryl (10 equiv) – H–H ↑

4 - Preparation of dibenzosiloles by intramolecular electrophilic C–H silylation:[6]

+ BArF –
R1 4 R1
[Ru]
R3P SAr
R = p-FC6H4
H H (1.0–3.0 mol %) Me
Si
Si Me Me
toluene
Me
140 °C (microwave)
– H–H ↑
R2 R2
1
R = Me, Cl, CF3, OSiR3, NR2
R2 = H, Cl

24
 No.174

5 - Direct formation of silyl enol ethers[7] and N-silylated enamines[8] by dehydrogenative coupling of enolizable ketones and
ketimines with hydrosilanes:

+ BArF –
Me2R3Si
O 4 O
H [Ru]
R3P SAr
R1 R1
R = Et or iPr
R2 (0.5 or 1.0 mol %) R2
or + Me2R3Si–H or
PG n-hexane or benzene Me2R3Si PG
N RT N
H – H–H ↑
R1 R1
R2 R2
R1 = alkyl, aryl R3 = Ph or Et
R2 = H, alkyl (1.0 equiv)

6 - Dehydrogenative silylation of the N–H bond of indoles, pyrroles, carbazoles, and anilines:[9]

+ BArF –
4
[Ru]
R1 Et3P SAr R1
(1.0 mol %)
+ Me2PhSi–H
N neat or n-hexane N
H RT–90 °C SiMe2Ph
indoles, pyrroles, (1.0 equiv) – H–H ↑
carbazoles, anilines
R1 = Me, Cl, Br, CF 3

7 - Regioselective hydrosilylation of pyridines and benzannulated congeners:[10]

R1 R1
+
N BArF4– N
[Ru]
pyridines, quinolines Et3P SAr SiMe2Ph
(1.0 mol %)
or + Me2PhSi–H or
neat
(1.0 equiv) RT
R1 R1

N N
SiMe2Ph
R2 R2 H
isoquinolines, phenanthridine
R1 = H, alkyl, aryl, F, Cl, Br, CF 3
R2 = H, Me

8 - Chemoselective hydrosilylation of carbon dioxide:[11]

+ BArF –
4
[Ru]
Et3P SAr
OSiEt3 OSiEt3
(1.0 mol %)
CO2 + EtMe2Si–H H + H
toluene OSiEt3 H
H H
5 bar
(18 % in Ar) 80 °C, 4 d 96 : 4 (85% yield)
150 °C, 16 d 3 : 97 (40% yield)

25
 No.174

9 - Hydrodefluorination of CF3-substitued anilines:[12]

+ BArF4–
[Ru]
R3P SAr
R = p-FC6H4
CF3 (10 mol %) CH3
NaOMe (5.0 mol %)
+ MePh2Si–H
n-hexane
R (4.4 equiv) 20–100 °C R

– MePh2Si–F

10 - Regioselective electrophilic C–H borylation of nitrogen-containing heterocycles:[13]

+
BArF4–
[Ru]
R3P SAr
H R = p-FC6H4 Bpin
R2 R2
(1.0 mol %)
+ pinB–H
N R1 neat N R1
Me 80 °C Me
– H–H ↑
R1 = H, Me (1.5 equiv) C3:C2 > 99:1
R2 = alkyl, NMe2, Br

References [7] C. D. F. Königs, H. F. T. Klare, Y. Ohki, K. Tatsumi, M.

Oestreich, Org. Lett. 2012, 14, 2842.
[1] Y. Ohki, Y. Takikawa, H. Sadohara, C. Kesenheimer, B. [8] J. Hermeke, H. F. T. Klare, M. Oestreich, Chem. Eur. J.
Engendahl, E. Kapatina, K. Tatsumi, Chem. Asian J. 2008, 2014, 20, 9250.
3, 1625. [9] C. D. F. Königs, M. F. Müller, N. Aiguabella, H. F. T.
[2] A. Lefranc, Z.-W. Qu, S. Grimme, M. Oestreich, Chem. Klare, M. Oestreich, Chem. Commun. 2013, 49, 1506.
Eur. J. 2016, 22, 10009. [10] C. D. F. Königs, H. F. T. Klare, M. Oestreich, Angew.
[3] T. Stahl, P. Hrobárik, C. D. F. Königs, Y. Ohki, K. Tatsumi, Chem. Int. Ed. 2013, 52, 10076.
S. Kemper, M. Kaupp, H. F. T. Klare, M. Oestreich, Chem. [11] T. T. Metsänen, M. Oestreich, Organometallics 2015, 34,
Sci. 2015, 6, 4324. 543.
[4] H. F. T. Klare, M. Oestreich, J.-i. Ito, H. Nishiyama, Y. [12] T. Stahl, H. F. T. Klare, M. Oestreich, J. Am. Chem. Soc.
Ohki, K. Tatsumi, J. Am. Chem. Soc. 2011, 133, 3312. 2013, 135, 1248.
[5] S. Wübbolt, M. Oestreich, Angew. Chem. Int. Ed. 2015, 54, [13] T. Stahl, K. Müther, Y. Ohki, K. Tatsumi, M. Oestreich, J.
15876. Am. Chem. Soc. 2013, 135, 10978.
[6] L. Omann, M. Oestreich, Angew. Chem. Int. Ed. 2015, 54,
10276.

Intoduction of the author:

Martin Oestreich
Professor Dr.
Institut für Chemie, Technische Universität Berlin

Martin Oestreich (born in 1971 in Pforzheim/Germany) received his diploma degree

with Paul Knochel (Marburg, 1996) and his doctoral degree with Dieter Hoppe (Münster,
1999). After a two-year postdoctoral stint with Larry E. Overman (Irvine, 1999–2001),
he completed his habilitation with Reinhard Brückner (Freiburg, 2001–2005) and was
appointed as Professor of Organic Chemistry at the Westfälische Wilhelms-Universität
Münster (2006–2011). He also held visiting positions at Cardiff University (Wales) and at
The Australian National University in Canberra. He has been Professor of Organic Chemistry at the Technische
Universität Berlin since 2011.
http://www.organometallics.tu-berlin.de/organometallics/menue/home/

TCI Related Products

C3327 [(DmpSR')RuCl(P-(i-Pr)3)] 100mg
C3328 [(DmpSR')RuCl(P-(4-Fluorophenyl)3)] 100mg

26