Journal of Organometallic Chemistry 694 (2009) 19431947

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Journal of Organometallic Chemistry

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Note

Synthesis, characterization, and catalytic application of a new chiral

P,N-indene ligand derived from (R)-BINOL
Dominik Wechsler a, Gabriele Schatte b, Mark Stradiotto a,*
a
b

Department of Chemistry, Dalhousie University, Halifax, NS, Canada B3H 4J3

Saskatchewan Structural Sciences Centre, University of Saskatchewan, Saskatoon, SK, Canada S7N 5C9

a r t i c l e

i n f o

Article history:
Received 4 February 2009
Received in revised form 17 February 2009
Accepted 18 February 2009
Available online 28 February 2009
Keywords:
Asymmetric catalysis
Chiral
Indene
P,N-ligand
Rhodium

a b s t r a c t
Lithiation of 2-dimethylaminoindene followed by quenching with [(R)-(1,10 -binaphthalene-2,20 diyl)]chlorophosphite and treatment with triethylamine afforded the crystallographically characterized
enantiopure P,N-indene 3 in 71% isolated yield. In the course of rhodium coordination chemistry studies
involving 3, the formation of the isolable complex [(j2-P,N-3)(j1-P,N-3)RhCl] (7) (81%) was observed,
thereby conrming the propensity of this new ligand to form LnRh(3)2 complexes. Such coordination
chemistry behavior may contribute in part to the generally poor catalytic performance exhibited by mixtures of 3 and rhodium precursor complexes in the asymmetric hydrogenation and hydrosilylation studies described herein.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Chiral platinum-group metal complexes are widely employed
as catalysts in the synthesis of chiral, non-racemic molecules on
both bench-top and industrial scales [1]. Notwithstanding the utility of enantiopure (often C2-symmetric) P,P- and N,N-ligands in
promoting such metal-mediated asymmetric transformations, related heterobidentate C1-symmetric P,N-ligands that combine soft
(P) and hard (N) donor fragments have in some cases been shown
offer inroads to reactivity that cannot be accessed by use of homobidentate ligand systems [2]. Indeed, the successful application of
heterobidentate chelates including the phosphinooxazoline
(PHOX) family of ligands [3] has prompted the development of
alternative classes of chiral P,N-ligands for use in promoting new
and/or challenging metal-mediated asymmetric substrate transformations [2].
In this context we have demonstrated that P,N-substituted indenes including 1-PiPr2-2-NMe2-indene (1; Scheme 1) can be employed in the synthesis of neutral, cationic, and formally
zwitterionic j2-P,N platinum-group metal complexes that are of
use as catalysts in the reduction of unsaturated substrates [4]. In
seeking to advance this research, we became interested in developing chiral variants of 1; given the well-established utility of enantiopure 1,10 -bi-2-naphthol (BINOL)-derived ligands including
MonoPhos [5] in platinum-group metal catalysis, we identied chi-

* Corresponding author. Tel.: +1 902 494 7190; fax: +1 902 494 1310.
E-mail address: [email protected] (M. Stradiotto).
0022-328X/$ - see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.02.015

ral P,N-substituted indenes prepared from (R)-BINOL (i.e. 2, or

alternatively the vinylic isomer 3) as attractive targets of inquiry
[6]. Herein we report on the synthesis and characterization of the
new chiral indene ligand 3, our efforts to develop the rhodium
coordination chemistry of this ligand, and the application of 3 in
rhodium-mediated asymmetric alkene hydrogenation and ketone
hydrosilylation.

2. Experimental
2.1. General considerations
All manipulations were conducted in the absence of oxygen and
water under an atmosphere of dinitrogen, either by use of standard
Schlenk methods or within an mBraun glovebox apparatus, utilizing glassware that was oven-dried (130 C) and evacuated while
hot prior to use. 2-Dimethylaminoindene 4 [7] and [(R)-(1,10 binaphthalene-2,20 -diyl)]chlorophosphite [8] were prepared by
use of literature procedures and were dried in vacuo for 24 h prior
to use. Otherwise, the purication and handling of reagents, as well
as the rhodium-catalyzed alkene hydrogenation and ketone hydrosilylation experiments, were carried out by using published protocols [9]. 1H, 13C, and 31P NMR characterization data were collected
at 300 K on a Bruker AV-500 spectrometer operating at 500.1,
125.8, and 202.5 MHz (respectively) with chemical shifts reported
in parts per million downeld of SiMe4 (for 1H and 13C) or 85%
H3PO4 in D2O (for 31P). 1H and 13C NMR chemical shift assignments
are made on the basis of data obtained from 13C DEPT, 1H1H COSY,

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D. Wechsler et al. / Journal of Organometallic Chemistry 694 (2009) 19431947

PiPr2

NMe2
H

O
H P

O
P

NMe2
H

O
NMe2

H H

Scheme 1.

H13C HSQC, and 1H13C HMBC NMR experiments. Elemental

analyses were performed by Canadian Microanalytical Service
Ltd., Delta, British Columbia, Canada.

clean conversion to 5. The THF and other volatile materials were

then removed in vacuo, and the residue was taken up in toluene.
The solution was then ltered through Celite followed by removal
of the toluene and other volatiles in vacuo and the solid was used
without further purication. 1H NMR (C6D6): d 7.50 (d,
3
JHH = 7.5 Hz, 1H, C7H), 7.277.20 (m, 2H, C4H and C6H), 7.03
(t, 3JHH = 7.5 Hz, 1H, C5H), 5.54 (s, 1H, C3H), 4.02 (d, 2JPH = 8.0 Hz,
1H, C1H), 3.042.91 (m, 4H, 2 CH2CH3), 2.862.74 (m, 4H, 2
CH2CH3), 2.61 (s, 6H, NMe2), 1.03 (m, 6H, 2 CH2CH3), 0.84 (m, 6H,
2 CH2CH3); 13C{1H} NMR (C6D6): d 160.0 (d, 2JPC = 6.7 Hz, C2),
146.8 (C7a), 138.8 (C3a), 126.1 (C6), 123.9 (d, 3JPC = 2.3 Hz, C7),
119.8 (C5), 117.7 (C4), 101.6 (C3), 53.0 (d, 1JPC = 42.6 Hz, C1), 43.4
(d, 2JPC = 19.2 Hz, 2 CH2CH3), 42.9 (d, 2JPC = 18.9 Hz, 2 CH2CH3),
41.9 (s, NMe2), 14.7 (2 CH2CH3), 14.1 (2 CH2CH3); 31P{1H} NMR
(C6D6): d 113.6.
2.4. Synthesis of 7

2.2. Synthesis of 3
A vial containing a magnetic stir bar was charged with 4 (0.14 g,
0.88 mmol) and 4 mL of toluene. The solution was cooled to 35 C
followed by the addition of n-BuLi (1.6 M in hexanes, pre-cooled to
35 C, 0.55 mL, 0.88 mmol). The mixture was stirred for 1 h at
ambient temperature. Meanwhile, a second vial was charged with
(0.31 g,
[(R)-(1,10 -binaphthalene-2,20 -diyl)]chlorophosphite
0.88 mmol) and 3 mL toluene. The solution of [(R)-(1,10 -binaphthalene-2,20 -diyl)]chlorophosphite was added dropwise to the solution of the indenyl lithium salt, followed by 2 h of stirring.
Triethylamine (0.49 mL, 3.5 mmol) was then added to the reaction
mixture, and the mixture was stirred overnight, during which time
a signicant quantity of solid 3 (including crystals suitable for Xray diffraction analysis) precipitated out of solution. The mixture
was then concentrated to near dryness and washed with benzene
(2 mL). The remaining solid was then dried in vacuo yielding 3 as
an analytically pure white solid (0.30 g, 0.63 mmol, 71%). Anal.
Calc. for C31H24PNO2: C, 78.63; H, 5.11; N, 2.96. Found: C, 78.40;
H, 4.95; N, 2.51%. 1H NMR (CD2Cl2): d 8.07 (d, 3JHH = 9.0 Hz, 1H,
CH Naph.), 8.02 (d, 3JHH = 8.5 Hz, 1H, CH Naph.), 7.91 (d,
3
JHH = 8.0 Hz, 1H, CH Naph.), 7.73 (d, 3JHH = 8.5 Hz, 1H, CH
Naph.), 7.59 (d, 3JHH = 8.5 Hz, 1H, CH Naph.), 7.557.45 (m, 4H,
CHs Naph.), 7.397.31 (m, 2H, CHs Naph.), 7.22 (d, 3JHH = 8.5 Hz,
1H, CH Naph.), 7.11 (d, 3JHH = 7.5 Hz, 1H, C7H), 6.59 (t,
3
JHH = 7.5 Hz, 1H, C5H or C6H), 6.10 (d, 3JHH = 8.0 Hz, 1H, C4
H), 6.02 (t, 3JHH = 7.5 Hz, 1H, C6H or C5H), 3.63 (s, 2H, CH2),
3.38 (d, 5JPH = 3.5 Hz, 6H, NMe2); 13C{1H} NMR (CD2Cl2): d 170.9
(d, 2JPC = 27.7 Hz, C2), 152.6 (quat Naph.), 151.6 (quat Naph.),
146.3 (C3a or C7a), 133.9 (C7a or C3a), 133.1 (quat Naph.), 133.0
(quat Naph.), 131.5 (quat Naph.), 131.1 (quat Naph.), 130.6 (CH
Naph.), 130.1 (CH Naph.), 128.4 (CH Naph.), 128.4 (CH Naph.),
128.2 (CH Naph.), 126.8 (CH Naph.), 126.5 (CH Naph.), 126.1
(CH Naph.), 125.9 (CH Naph.), 125.5 (C6 or C5), 124.7 (CH
Naph.), 124.3 (CH Naph.), 123.0 (quat), 122.2 (CH Naph.),
121.8 (C7), 121.5 (C4), 120.3 (C5 or C6), 70.6 (quat), 45.5 (d,
4
JPC = 23.0 Hz, NMe2), 41.1 (d, 3JPC = 4.4 Hz, CH2); 31P{1H} NMR
(CD2Cl2): d 197.4.
2.3. Formation and characterization of 5
A vial containing a magnetic stir bar was charged with 4 (0.40 g,
0.25 mmol) and 2 mL of THF. The mixture was cooled to 35 C,
and magnetic stirring was initiated followed by the dropwise addition of n-BuLi (1.6 M in hexanes, pre-cooled to 35 C, 0.16 mL,
0.25 mmol). Following the addition, the resulting mixture was stirred for 1 h. To the reaction mixture was then added (Et2N)2PCl by
using an Eppendorf pipette, followed by stirring for 3.5 h. 31P NMR
data obtained from an aliquot of the reaction mixture indicated the

A vial containing a magnetic stir bar was charged with 3

(0.044 g, 0.094 mmol) and 3 mL of THF. To a separate vial,
[(COE)2RhCl]2 (0.017 g, 0.024 mmol) and THF (2 mL) were added.
The rhodium-containing solution was added to the THF slurry of
3 and magnetically stirred for 2 h. The solvent was then removed
in vacuo, and the residue washed with pentane. Any residual solvent and other volatiles were removed in vacuo, leaving behind 7
as a light brown solid (0.041 g, 0.038 mmol, 81%). Anal. Calc. for
C62H48P2N2O4RhCl: C, 68.59; H, 4.46; N, 2.58. Found: C, 68.67; H,
4.46; N, 2.29%. 1H NMR (C6D6): d 9.52 (d, 3JHH = 7.4 Hz, 1H, aryl
CH), 8.61 (d, 3JHH = 8.7 Hz, 1H, aryl CH), 7.89 (d, 3JHH = 8.8 Hz,
1H, aryl CH), 7.80 (d, 3JHH = 8.1 Hz, 1H, aryl CH), 7.637.69 (m,
2H, aryl CHs), 7.59 (t, 3JHH = 7.3 Hz, 1H, aryl CH), 7.417.52 (m,
4H, aryl CHs), 7.25 (d, 3JHH = 8.7 Hz, 1H, aryl CH), 7.137.17 (m,
1H, aryl CH), 7.037.07 (m, 2H, aryl CHs), 6.987.02 (m, 2H, aryl
CHs), 6.97 (d, 3JHH = 8.8 Hz, 1H, aryl CH), 6.666.83 (m, 5H, aryl
CHs), 6.51 (m, 1H, aryl CH), 6.43 (m, 1H, aryl CH), 6.11 (t,
3
JHH = 7.4 Hz, 1H, aryl CH), 6.06 (d, 3JHH = 6.0 Hz, 1H, aryl CH),
5.67 (d, 3JHH = 8.9 Hz, 1H, aryl CH), 5.42 (d, 3JHH = 8.9 Hz, 1H, aryl
CH), 5.23 (d, 3JHH = 7.8 Hz, 1H, aryl CH), 5.21 (s, 1H, aryl CH),
3.10 (s, 3H, bound NMe), 2.86 (s, 3H, bound NMe), 2.482.34 (m,
4H, CH2), 1.98 (s, 6H, unbound NMe2); 13C{1H} NMR (C6D6): d
176.4 (j2-P,N ligand C2), 156.8 (j1-P,N ligand C2), 156.7 (quat),
151.4 (quat), 151.3 (quat), 151.1 (quat), 150.7 (quat), 150.2 (quat),
149.8 (quat), 149.7 (quat), 148.0 (quat), 147.9 (quat), 142.3 (C3a or
C7a), 137.2 (quat), 134.8 (quat), 133.6 (quat), 133.2 (quat), 132.3
(quat), 131.9 (quat), 131.8 (quat), 131.4 (quat), 131.0 (quat),
130.3 (aryl CH), 130.0 (quat), 129.1 (aryl CH), 128.4 (aryl CH),
128.2 (aryl CH), 128.0 (aryl CH), 127.3 (aryl CH), 127.2 (aryl
CH), 127.1 (2 aryl CHs), 126.8 (aryl CH), 126.7 (aryl CH),
126.0 (aryl CH), 125.8 (aryl CH), 125.5 (aryl CH), 125.3 (aryl
CH), 125.1 (2 aryl CHs), 125.0 (aryl CH), 124.6 (aryl CH),
124.5 (2 aryl CHs), 123.9 (aryl CH), 123.7 (aryl CH), 123.5 (aryl
CH), 122.7 (aryl CH), 122.4 (aryl CH), 121.6 (aryl CH), 120.2
(aryl CH), 117.2 (aryl CH), 103.4 (aryl CH), 55.7 (aryl CH),
55.6 (aryl CH), 50.7 (bound NMe), 48.5 (bound NMe), 40.8 (unbound NMe2), 29.7 (CH2), 29.6 (CH2); 31P{1H} NMR (C6D6): d
199.4 (d of d, 2JPP = 36.4 Hz, 1JRhP = 261.2 Hz), 170.3 (d of d,
2
JPP = 36.4 Hz, 1JRhP = 291.6 Hz).
2.5. Crystallographic solution and renement details for 3
Crystallographic data for this compound were obtained at
173(2) K on a Nonius KappaCCD 4-Circle Kappa FR540C diffractometer using a graphite-monochromated Mo Ka (k = 0.71073 )
radiation, employing a sample that was mounted in inert oil and
transferred to a cold gas stream on the diffractometer. Cell parameters were initially retrieved using the COLLECT software (Nonius),

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D. Wechsler et al. / Journal of Organometallic Chemistry 694 (2009) 19431947

and rened with the HKL DENZO and SCALEPACK software [10]. Data
reduction and absorption correction (multi-scan) were also performed with the HKL DENZO and SCALEPACK software. The structure
was solved by using direct methods, and rened by use of full-matrix least-squares procedures (on F2) with R1 based on F 2o  2rF 2o
and wR2 based on F 2o  3rF 2o . Anisotropic displacement parameters were employed throughout for the non-H atoms, and all Hatoms were added at calculated positions and rened by use of a
riding model employing isotropic displacement parameters based
on the isotropic displacement parameter of the attached atom.
The near-zero nal rened value of the absolute structure parameter supported that the correct absolute structure had been chosen
[11]. The crystal structure diagram in Fig. 1 was generated by use
of the ORTEP-3 for Windows program [12].

H
NMe2

1. n-BuLi
2. (Et2N) 2PCl

NMe2

P(NEt 2)2

(R)-BINOL

O
O

P NEt2

+ 4
+ HNEt 2

6
Scheme 2.

3. Results and discussion

3.1. Synthetic investigations
The conversion of (sp2-R)P(NEt2)2 precursors into (sp2-R)P(BINOL-2H) and HNEt2 upon treatment with BINOL has been successfully exploited in the synthesis of a range of chiral phosphoruscontaining compounds [13]. Using this approach, 2-dimethylaminoindene 4 was lithiated, followed by quenching with ClP(NEt2)2
to give 1-P(NEt2)2-2-NMe2-indene 5 (Scheme 2). While 5 was completely consumed over the course of 24 h upon reaction with (R)BINOL in reuxing toluene, 1H and 31P NMR analysis of the reaction
mixture revealed an equimolar mixture of 4, the known phosphoramidite 6 [14], and HNEt2, rather than the desired product 2 (or
the isomer 3). This product mixture can be viewed as arising from
a combination of the desired protonolysis by (R)-BINOL of a PN
linkage in 5, accompanied by unwanted P-C(sp3) bond protonolysis. Given that previously reported synthetic protocols of this type
have employed precursors that feature more robust P-C(sp2) linkages [13], we sought to promote the isomerization of the allylic
phosphine 5 to the vinylic phosphine 3-P(NEt2)2-2-NMe2-indene;
unfortunately, we were unable to effect the clean isomerization

H
NMe2
H

1. n-BuLi
2. (RO)2PCl
3. NEt3

O
P

O
NMe2

H H

Scheme 3.

of 5 by use of heating and/or treatment with triethylamine [6a].

As such, alternative synthetic inroads to 2 (or 3) were explored.
In using a protocol similar to that employed in the synthesis of 1
[15], compound 4 was lithiated, followed by quenching with [(R)(1,10 -binaphthalene-2,20 -diyl)]chlorophosphite (represented as
(RO)2PCl in Scheme 3). Whereas a mixture of phosphorus-containing products was formed initially (including 3; 31P NMR), treatment of this reaction mixture with triethylamine promoted the
conversion of at least one of these products (possibly correspond-

Table 1
Crystallographic data for 3.
Empirical formula
Formula weight
Crystal dimensions (mm3)
Color, habit
Crystal system
Space group
a ()
b ()
c ()
a ()
b ()
c ()
V (3)
Z
Range of transmission
2h Limit ()

Fig. 1. ORTEP diagram of 3, shown with 50% displacement ellipsoids and with the
indene atomic numbering scheme depicted; selected H-atoms have been omitted
for clarity. Selected bond lengths () and angles () for 3: PC3 1.777(3); PO1
1.671(3); PO2 1.669(2); NC2 1.351(4); NCHa3 1:4674; NCHb3 1:4555; C1
C2 1.511(4); C2C3 1.399(4); C2NCHa3 120:83; C2NCHb3 123:23; CHa3
NCHb3 115:73.

Independent reections
Observed reections
Data/restraints/parameters
Goodness-of-t
Absolute structure parameter
R1 F 2o  2rF 2o 
wR2 F 2o  3rF 2o 
Largest peak, hole (e 3)

C31H24N1O2P1
473.82
0.20  0.20  0.10
Colorless, plate
Monoclinic
P21
9.4950(6)
7.2100(4)
17.9760(8)
90
103.444(3)
90
1196.90(11)
2
0.98570.9716
52.74
11 6 h 6 11
8 6 k 6 9
22 6 l 6 22
4656
3840
4656/1/319
1.057
0.08(14)
0.0561
0.1331
0.257, 0.270

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D. Wechsler et al. / Journal of Organometallic Chemistry 694 (2009) 19431947

ing to 2) into 3. The P,N-indene 3 was obtained as an analytically

pure white solid in 71% isolated yield. To complement the solution
spectroscopic characterization of 3, a single-crystal X-ray diffraction experiment was conducted; an ORTEP [12] diagram of 3 is presented in Fig. 1 and crystallographic data are collected in Table 1.
The overall geometric features in 3 are comparable to those of
the related achiral compound 3-PPh2-2-NMe2-indene [6a]. Notably, the apparent co-planarity of the non-hydrogen indene and
dimethylamino atoms, the relatively short NC2 distance
(1.351(4) ), and the sum of the angles at nitrogen (ca. 360), collectively indicate that the lone pair of electrons on nitrogen in 3 is
in conjugation with the indene p-system. Furthermore, the absolute conguration observed in the crystallographically characterized sample of 3 served to conrm that the stereochemistry of
the (R)-BINOL synthon is retained in this new P,N-substituted
indene.
Having successfully prepared the new chiral P,N-indene ligand
3, we turned our attention to the preparation of rhodium coordination complexes. However, unlike 1-PiPr2-2-NMe2-indene (1),
which served as a precursor to the cationic complexes [(COD)
Rh(j2-1/3-PiPr2-2-NMe2-indene)]+X (COD = g4-1,5-cyclooctadiene), as well as the related zwitterion (COD)Rh(j2-3-PiPr2-2NMe2-indenide) [4c,15], rather complex reactivity was observed
when employing 3 under similar conditions. In this regard, treatment of 3 with either [(COD)RhCl]2 or in situ generated
[(COD)Rh(THF)2]+X afforded an intractable mixture of products.
Furthermore, our efforts to generate an indenyl salt of 3 by use
of reagents such as n-BuLi or NaN(SiMe3)2 under conditions that
proved effective for the metalation of 1, invariably resulted in the
formation of complex reaction mixtures. Although we are presently uncertain as to the identity of the products formed in the latter metalation reactions involving 3, it is possible that PO bond
cleavage occurs in the presence of the alkali metal reagents
employed.
In exploring the reactivity of [(COE)2RhCl]2 (COE = g2-cyclooctene) with 3, a 2:1 ligand-to-metal complex 7 was formed invariably (31P NMR), even when using a 1:1 stoichiometry of 3:Rh
(Scheme 4); complex 7 was also generated cleanly when using a
2:1 ratio of 3 and (PPh3)3RhCl. Complex 7 was obtained as an analytically pure light brown solid in 81% isolated yield, and was characterized spectroscopically. Our assignment of 7 as featuring both
j2-P,N-3 and j1-P,N-3 ligands in which the phosphorus atoms are
cis-disposed is in keeping with the observation of two 31P NMR resonances that exhibit relatively small 2JPP values (36.4 Hz). This
structural assignment is also consistent with the observation of
distinct 1H and 13C NMR resonances for each of the inequivalent
methyl groups of the j2-P,N-3 ligand, as well as a single set of resonances for the methyl groups of the j1-P,N-3 ligand which are
rendered equivalent by rotation and inversion processes at nitrogen [4c] that are rapid on the NMR timescale. In light of our limited
success in preparing isolable rhodium complexes of 3, asymmetric

Me2N
O O

0.25 [(COE)2RhCl] 2

or 0.5 (PPh3) 3RhCl

H

N
Me2

Scheme 4.

Cl

O
O

Rh

Table 2
Hydrogenation of methyl-2-acetamidoacrylate.a

O
H2

O
NH
O

*
NH

catalyst
O

O
(1)

Entry

Mol% 3 added

Solvent

%b

% eec

2-1
2-2
2-3
2-4

0
6.0
6.0
12.0

THF
THF
CH2Cl2
THF

>99
>99
26
32

<5
40
<5
67

a
Conditions: 24 C; 1 atm H2; 5.0 mol% CODRhTHF2  BF
4 prepared in situ
from 0.5 [(COD)MCl]2 and AgBF4 in THF (COD = g4-1,5-cyclooctadiene).
b
Percent conversion based on the consumption of methyl-2-acetamidoacrylate
(8) at 24 h.
c
Enantiomeric excess of 9 determined on the basis of chiral GC-FID data [9].

hydrogenation and hydrosilylation studies (vide infra) were conducting by using primarily catalyst mixtures that were prepared
in situ.
3.2. Asymmetric hydrogenation
The rhodium-mediated asymmetric hydrogenation of methyl2-acetamidoacrylate 8 to afford 9 (Eq. (1)) under mild conditions
(24 C, ca. 1 atm H2, 5.0 mol% Rh) was selected as a test reaction
to use in benchmarking the catalytic performance of 3 [16]; representative results of these hydrogenation studies are collected in
Table 2. Control experiments conrmed the ability of catalyst mixtures derived from 0.5 [(COD)RhCl]2 and AgBF4 in THF (without
added 3) to efciently mediate the reduction of 8 (entry 2-1). Under analogous conditions employing 6.0 mol% 3 (1.2 equiv. relative
to rhodium) in THF, the quantitative hydrogenation of 8 was also
achieved, affording 9 in a modest 40% ee (entry 2-2); inferior performance was observed in dichloromethane (entry 2-3). While
increasing the amount of 3 to 12.0 mol% provided a rise in enantioselectivity in THF (67% ee; entry 2-4), such gains were made at the
expense of catalyst productivity (32% conversion). Negligible conversion was achieved by using 6.0 mol% of the isolable Rh complex
7 in either THF or CH2Cl2 under similar experimental conditions.
3.3. Asymmetric hydrosilylation
In an effort to evaluate further the catalytic utility of 3, we
turned our attention to the asymmetric hydrosilylation of ketones
[17] a challenging transformation for which rhodium catalysts
supported by appropriately designed chiral j2-P,N ligands have
proven to be highly effective [18]. Representative results of our catalytic investigations examining the asymmetric hydrosilylation of
acetophenone with Ph2SiH2 (Eq. (2)) are collected in Table 3. In
preliminary experiments conducted in THF using catalyst mixtures
comprised of 2.5 mol% [(COD)RhCl]2 or [(COE)2RhCl]2 and 6.0 mol%
3, conversions of 74% and 63% were achieved (entries 3-1 and 3-2).
Altering the conditions to promote the formation of 7 as a pre-catalyst (2.5 mol% [(COE)2RhCl]2 and 12.0 mol% 3) offered no reactivity advantages (55%; entry 3-3), and the catalytic performance of
pre-formed 7 proved to be identical to this in situ prepared catalyst
mixture. While related cationic rhodium catalyst systems did not
offer signicantly improved performance in THF (3066%; entries
3-4 to 3-7), in moving to dichloromethane and employing 3:Rh
in an equilmolar ratio, somewhat higher conversions were
achieved (5793%; entries 3-8 to 3-11). However, despite the range

D. Wechsler et al. / Journal of Organometallic Chemistry 694 (2009) 19431947

bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/j.jorganchem.
2009.02.015.

Table 3
Addition of diphenylsilane to acetophenone.

OH

Ph2SiH2

H+

Ph

catalyst

H2O

Entry

Metal precursora (5.0 mol% Rh)

Mol% 3 added

Solvent

%b

3-1
3-2
3-3
3-4
3-5
3-6
3-7
3-8
3-9
3-10
3-11

[(COD)RhCl]2
[(COE)2RhCl]2
[(COE)2RhCl]2
CODRhTHF2  BF
4
CODRhTHF2  BF
4

COE2 RhTHF2  BF

4
CODRhTHF2  BF
4
[(COD)RhCl]2
[(COE)2RhCl]2
CODRhTHF2  BF
4
CODRhTHF2  BF
4

6.0
6.0
12.0
6.0
12.0
6.0
12.0
6.0
6.0
6.0
6.0

THF
THF
THF
THF
THF
THF
THF
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2

74
63
55
66
52
50
30
84
57
93
90

Ph *
10

1947

(2)


a
CODRhTHF2  BF
4 and COE2 RhTHF2  BF4 prepared in situ from 0.5
[(COD)RhCl]2 and 0.5 [(COE)2RhCl]2 (respectively) and AgBF4 in THF (COD = g4-1,5cyclooctadiene; COE = cyclooctene).
b
Percent conversion to 10 (following workup) after 18 h at 24 C; the enantiomeric excess of 10 (in all cases 610%) was determined on the basis of chiral GC-FID
data [9].

of conditions and pre-catalyst mixtures surveyed, negligible

enantioselectivities (<10% ee) were attained in these reactions.
4. Summary and conclusions
In conclusion, we have reported herein on the synthesis and
characterization of a new enantiopure heterobidentate P,N-indene
ligand 3 that is derived from (R)-BINOL. In contrast to the established ability of 1/3-PiPr2-2-NMe2-indene to give rise to isolable
neutral, cationic, and formally zwitterionic j2-P,N rhodium coordination complexes in high yield, more complex reactivity was observed for 3. In the course of these coordination chemistry
studies, the formation of the isolable complex [(j2-P,N-3)(j1-P,N3)RhCl] (7) was observed, thereby conrming the propensity of this
new ligand to form LnRh(3)2 complexes; such ligation behavior
may contribute in part to the generally poor catalytic performance
exhibited by mixtures of 3 and rhodium precursor complexes in
the asymmetric hydrogenation and hydrosilylation studies reported herein.
Acknowledgements
Acknowledgment is made to Dalhousie University and the Natural Sciences and Engineering Research Council of Canada for their
generous support of this work. We also thank Drs. Michael Lumsden and Katherine Robertson (Atlantic Region Magnetic Resonance
Center, Dalhousie) for assistance in the acquisition of NMR data.
Appendix A. Supplementary material
CCDC 719217 contains the supplementary crystallographic data
for 3. These data can be obtained free of charge from The Cam-

References
[1] (a) N.B. Johnson, I.C. Lennon, P.H. Moran, J.A. Ramsden, Acc. Chem. Res. 40
(2007) 1291;
(b) V. Farina, J.T. Reeves, C.H. Senanayake, J.J. Song, Chem. Rev. 106 (2006)
2734;
(c) H.-U. Blaser, B. Pugin, F. Spindler, J. Mol. Catal. A 231 (2005) 1;
(d) H.-U. Blaser, F. Spindler, M. Studer, Appl. Catal. A 221 (2001) 119.
[2] (a) K. Kllstrm, I. Munslow, P.G. Andersson, Chem. Eur. J. 12 (2006) 3194;
(b) P.J. Guiry, C.P. Saunders, Adv. Synth. Catal. 346 (2004) 497;
(c) G. Chelucci, G. Orr, G.A. Pinna, Tetrahedron 59 (2003) 9471;
(d) K.N. Gavrilov, A.I. Polosukhin, Russ. Chem. Rev. 69 (2000) 661.
[3] (a) A. Pfaltz, W.J. Drury III, Proc. Natl. Acad. Sci. 101 (2004) 5723;
(b) G. Helmchen, A. Pfaltz, Acc. Chem. Res. 33 (2000) 336.
[4] (a) R.J. Lundgren, M.A. Rankin, R. McDonald, M. Stradiotto, Organometallics 27
(2008) 254;
(b) R.J. Lundgren, M.A. Rankin, R. McDonald, G. Schatte, M. Stradiotto, Angew.
Chem., Int. Ed. 46 (2007) 4732;
(c) J. Cipot, R. McDonald, M.J. Ferguson, G. Schatte, M. Stradiotto,
Organometallics 26 (2007) 594.
[5] (a) L. Eberhardt, D. Armspach, J. Harroweld, D. Matt, Chem. Soc. Rev. 37
(2008) 839;
(b) A.J. Minnaard, B.L. Feringa, L. Lefort, J.G. de Vries, Acc. Chem. Res. 40 (2007)
1267;
(c) J.G. de Vries, L. Lefort, Chem. Eur. J. 12 (2006) 4722.
[6] (a) We viewed 2 and 3 as being equally suitable ligand targets, in light of our
observation that the introduction of the allylic phosphine 1-PiPr2-2-NMe2indene 1, or alternatively mixtures of 1 and the vinylic phosphine 3-PiPr2-2NMe2-indene, to a transition metal fragment is often accompanied by ligand
isomerization to give coordination complexes of 3-PiPr2-2-NMe2-indene. For
discussions of such ligand isomerization phenomena, see: J. Cipot, D. Wechsler,
M. Stradiotto, R. McDonald, M.J. Ferguson, Organometallics 22 (2003) 5185;
(b) Ref. [4] herein.
[7] (a) U. Edlund, G. Bergson, Acta Chem. Scand. 25 (1971) 3625;
(b) J. Klosin, W.J. Kruper Jr., P.N. Nickias, G.R. Roof, P. De Waele, K.A. Abboud,
Organometallics 20 (2001) 2663.
[8] R. Sablong, C. Newton, P. Dierkes, J.A. Osborn, Tetrahedron Lett. 37 (1996)
4933.
[9] D. Wechsler, M. Stradiotto, Can. J. Chem. 87 (2009) 72.
[10] HKL DENZO and SCALEPACK v1.96: Z. Otwinowski, W. Minor, in: C.W. Carter, R.M.
Sweet (Eds.), Macromolecular Crystallography, Part A, vol. 276, Academic
Press, San Diego, 1997, pp. 307326.
[11] The Flack absolute structure parameter will rene to a value near zero if the
structure is in the correct conguration and will rene to a value near one for
the inverted conguration: H.D. Flack, G. Bernardinelli, J. Appl. Crystallogr. 33
(2000) 1143.
[12] ORTEP-3 for Windows Version 1.074: L.J. Farrugia, J. Appl. Crystallogr. 30
(1997) 565.
[13] (a) Selected recent examples: D. Sirbu, G. Consiglio, S. Gischig, J. Organomet.
Chem. 691 (2006) 1143;
(b) I.D. Kostas, K.A. Vallianatou, J. Holz, A. Brner, Appl. Organomet. Chem. 19
(2005) 1090;
(c) G. Franci, D. Drommi, C. Graiff, F. Faraone, A. Tiripicchio, Inorg. Chim. Acta
338 (2002) 59;
(d) M.T. Reetz, D. Moulin, A. Gosberg, Org. Lett. 3 (2001) 4083.
[14] L.A. Arnold, R. Imbos, A. Mandoli, A.H.M. de Vries, R. Naasz, B.L. Feringa,
Tetrahedron 56 (2000) 2865.
[15] M. Stradiotto, J. Cipot, R. McDonald, J. Am. Chem. Soc. 125 (2003) 5618.
[16] I.D. Gridnev, T. Imamoto, Acc. Chem. Res. 37 (2004) 633.
[17] H. Brunner, in: M. Beller, C. Bolm (Eds.), Transition Metals for Organic
Synthesis, vol. 2, Wiley-VCH, New York, 1998, pp. 131140.
[18] (a) For some noteworthy examples, see: B. Tao, G.C. Fu, Angew. Chem., Int. Ed.
41 (2002) 3892;
(b) D.K. Heldmann, D. Seebach, Helv. Chim. Acta 82 (1999) 1096;
(c) Y. Nishibayashi, K. Segawa, K. Ohe, S. Uemura, Organometallics 14 (1995)
5486.