Structural and spectroscopic characterization of an unprecedented cationic transition-metal η1-silane complex

Article abstract of DOI:10.1002/anie.200705359

No room for side-on: In the complex shown, Et₃SiH is bound to the cationic Ir^III center in an unprecedented end-on fashion through the Si-H bond with no appreciable metal-silicon interaction (white H, green Si, pink Ir, red O, orange P, gray C). The long Ir...Si distance of 3.346(1) U is 0.97 A greater than the sum of the covalent radii of Ir and Si. DFT studies indicate that the tBu substituents on the bidentate phosphorus ligand dictate the coordination mode of the silane. (Figure Presented)

Full text of DOI:10.1002/anie.200705359

Angewandte
Chemie
DOI: 10.1002/anie.200705359
h1-Silane Complex
Structural and Spectroscopic Characterization of an Unprecedented
Cationic Transition-Metal h1-Silane Complex**
Jian Yang, Peter S. White, Cynthia K. Schauer,* and Maurice Brookhart*
Understanding the coordination of s bonds to metal centers is
of fundamental importance and provides insights useful for
developing metal-catalyzed transformations.[1] s-Complexes
between silanes and cationic transition-metal compounds
possess highly electrophilic silicon centers and are invoked as
[2,3]
À
key intermediates in catalytic Si H activation reactions.
There are examples of isolated neutral silane s-complexes,
but cationic complexes of this type are rarely isolable
presumably due to the extreme sensitivity of the electrophilic
Si center to nucleophiles.[4,5] Moreover, all of the structurally
characterized s-complexes are h2-SiH complexes, in which the
silane is bound side-on with significant metal–silicon inter-
action (Scheme 1, B).[6,7] We report here the first example of a
fully characterized cationic transition-metal h1-silane complex
(Scheme 1, A) in which the silane is bound to a metal center in
an end-on fashion with no appreciable metal–silicon inter-
action.
to a bridging (Ir-H-Si) hydride while the triplet at d =
À44.2 ppm (2JP-H = 11.6 Hz) is assigned to a terminal (Ir-H)
hydride. The upfield shift of d = À44.2 ppm is indicative of a
hydride trans to a vacant coordination site.[9] These NMR
data, especially the JSi-H value,[10] suggest that 2 is a square-
pyramidal Et3SiH s-complex with an apical hydride and
silane bound in the square plane.
An X-ray quality crystal of 2 was obtained by slow
diffusion of pentane into a C6H5F solution of 1 and excess
Et3SiH at 258C under Ar. The ORTEP diagram of 2 is shown
in Figure 1.[11] Et3SiH is coordinated trans to the ipso carbon
Scheme 1. Interactions of R3SiH with transition-metal complexes.
During our studies of Ir-catalyzed reduction of alkyl
halides by triethylsilane, a cationic iridium(III)–Et3SiH s-
complex, originally formulated as an h2-SiH complex, was
proposed as a key intermediate.[2a] This intermediate can be
generated in situ by treatment of [(POCOP)Ir(H)-
(acetone)]+[B(C6F5)4]À (1; POCOP = 2,6-[OP(tBu)2]2C6H3)
with Et3SiH in CD2Cl2 at 238C [Eq. (1)].[8]
At 238C, the 1H NMR resonances for the terminal (Ir-H)
and bridging (Ir-H-Si) hydrides are too broad to be observed
due to exchange. At À708C, the static spectrum is obtained
which shows two hydride resonances in a 1:1 ratio. The singlet
at d = À4.9 ppm with 29Si satellites (1JSi-H = 79 Hz) is assigned
Figure 1. An ORTEP diagram of the cation in 2 (hydrogen atoms
omitted). Key interatomic distances [Š] and bond angles [8]: Ir1–C3
2.015(2), Ir1–P2 2.3091(6), Ir1–P1 2.3470(6), Ir1–H1 1.94(3), Ir1–H2
1.425(18), Si1–H1 1.48(3); Ir1···Si1 3.346(1), Ir1-H1-Si1 157(1), P2-Ir1-
P1 158.06(2).
[*] J. Yang, Dr. P. S. White, Prof. C. K. Schauer, Prof. M. Brookhart
Department of Chemistry, University of North Carolina, Chapel Hill
Chapel Hill, NC 27599-3290 (USA)
of the tridentate POCOP backbone. The hydrogens bound to
Ir were located in the final difference map, and their refined
positions are consistent with a square-pyramidal geometry at
E-mail: schauer@unc.edu
1
Ir assigned using H NMR data. The most striking structural
mbrookhart@unc.edu
feature of 2 is the orientation of the coordinated silane ligand,
characterized by a long Ir···Si distance of 3.346(1) Š (0.97 Š
greater than the sum of the covalent radii of Ir and Si)[12] and
an Ir-H-Si angle of 1578, both indicative of an end-on h1-H(Si)
[**] We gratefully acknowledge funding by the STC program of the
National Science Foundation under agreement No. CHE-9876674.
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
Angew. Chem. Int. Ed. 2008, 47, 4141 –4143
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4141

Communications
coordination mode of the silane. In h2-SiH complexes, the M–
corresponding to different rotamers about the Ir H and Si H
bonds. For each complex, structural data are presented for
two distinct minima in which the SiMe3 group is oriented
proximal and distal to the hydride ligand (e.g., Figure 2, 4p
and 4d, respectively). The calculated structure for 3d agrees
well with expectations based on X-ray data. The hydride
ligand occupies the apical site in the square pyramid (Ir–H
1.54 Š). The hydrogen of the silane is positioned approx-
imately trans to C(aryl) (Ir–H(Si) 1.87 Š). The Si–H distance
of 1.57 Š is ca. 0.08 Š longer than the calculated Si–H
À
À
Si distances remain relatively short.[4c,b,5a]
To provide insight into the structural and bonding features
of the h1-H(Si) binding mode, DFT studies[13] were performed
on the HSiMe3 analogue of 2 (3), as well as the HSiMe3
complex of model systems in which Me replaces all four tBu
groups (4), and Me replaces two cis tBu groups distal to the
hydride ligand (5). Selected metric parameters for the
calculated minima are listed in Table 1 and selected minima
for 3 and 4 are shown in Figure 2. The potential energy
surfaces for the silane complexes show multiple minima
À
distance in the parent silane, reflecting activation of the Si H
bond. The calculated Ir···Si non-bonding distance of 3.38 Š
for 3d is similar to the X-ray distance of 3.35 Š. The
corresponding Ir-H1-Si angle is 1618. An Ir-H1-Si angle of
1808 might be expected for an h1-H(Si) interaction. The space-
filling diagram for 3d (Figure 2) shows close contact between
the SiMe groups and the Me groups on the tBu substituents,
and these interactions, together with similar close interactions
on the opposite face apparently dictate the Ir-H1-Si angle
adopted in 2.
Table 1: Selected bond lengths [Š] and angles [8] and energies from DFT
studies.
Cmpd
Ir-H1
Si-H1[a]
Ir···Si
Ir-H1-Si
Erel
[kcalmolÀ1 [b]
]
3p
3d
4p
4d
4d’
5d
5d’
1.865
1.870
1.785
1.753
1.751
1.757
1.752
1.572
1.572
1.576
1.605
1.653
1.609
1.646
3.379
3.395
3.169
2.887
2.619
2.871
2.626
158.7
161.0
141.1
118.5
100.5
117.0
101.2
0.0
À0.1
0.0
À0.9
À1.9
0.0
The reduced ligand steric bulk in trimmed 4 allows the
silicon in 4d to more closely approach Ir (Ir···Si 2.89 Š).
Moreover, 4 shows a distinct minimum (4d’) with an even
shorter Ir–Si distance (Ir···Si 2.62 Š), in which the silane
coordination is assisted by the formation of an axial agostic
interaction with a SiMe group (Figure 2) (H···Ir 2.25 Š). The
development of the h2-SiH interaction is demonstrated by the
structural parameters of the series of complexes, 4p, 4d, and
4d’, with progressively longer H1–Si distances, shorter Ir–H1
and Ir–Si distances, and smaller Ir-H1-Si angles along the
series (see Table 1). The relative energies of 4p, 4d, and 4d’
are 0, À0.9, and À1.9 kcalmolÀ1, respectively, indicating that
the stabilization afforded by the h2-SiH interaction is small.
Trimmed 5 is electronically intermediate between 3 and 4.
The similar structural parameters and energetics of the d and
d’ minima for 4 and 5 are consistent with the assertion that the
steric properties of the ligand are driving the structural
changes in the trimmed complexes.
À0.9
[a] The calculated Si–H distance in HSiMe3 is 1.493 Š. [b] Difference in
electronic energies.
An NBO analysis[14] was conducted on the silane com-
plexes, and the natural charges are shown in Table 2.
Formation of the h1-H(Si) silane complex increases the
À
polarization of the Si H bond, with an accompanying
increase in charge on silicon by ca. 0.2 in comparison to the
free silane, and a decrease in the charge on hydrogen.
Table 2: Natural charges and NBO populations in the silane
complexes.[a]
Natural Charges
Si H(Si)
NBO Populations
s Si-H s* Ir-C Ir(dp*) s* Si-H
Ir
3p
3d
0.021 1.563 À0.281 1.796
0.011 1.554 À0.275 1.796
0.313
0.313
0.336
0.380
0.426
0.376
0.429
1.952
1.954
1.947
1.931
1.916
1.933
1.916
0.063
0.063
0.071
0.084
0.093
0.079
0.092
4p À0.011 1.540 À0.255 1.763
4d À0.051 1.476 À0.175 1.712
4d’ À0.116 1.441 À0.115 1.673
5d À0.038 1.490 À0.180 1.720
5d’ À0.123 1.449 À0.115 1.674
Figure 2. Selected minima for 3 and 4, and corresponding space-filling
diagrams (topview).
[a] In HSiMe3, the natural charges on Si and H are 1.345 and À0.196,
respectively.
4142
www.angewandte.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2008, 47, 4141 –4143

Angewandte
Chemie
Adoption of the h2-SiH coordination mode reduces the
positive charge on silicon, and increases the charge on
hydrogen. Therefore the h1-H(Si) coordinated silane, with
little Ir to SiH s* backbonding, is expected be a more potent
source of electrophilic silicon than an h2-SiH complex. The
NBO populations of the relevant orbitals for interaction with
the silane (see Figure 3) are summarized in Table 2. The NBO
6453 – 6459; c) G. J. Kubas, Catal. Lett. 2005, 104, 79 – 101;
d) G. J. Kubas, Adv. Inorg. Chem. 2004, 56, 127 – 177; e) M.
Buhl, F. T. Mauschick, Organometallics 2003, 22, 1422 – 1431;
f) X. Fang, J. Huhmann-Vincent, B. L. Scott, G. J. Kubas, J.
Organomet. Chem. 2000, 609, 95 – 103; g) S. Chang, E. Scharrer,
M. Brookhart, J. Mol. Catal. A 1998, 130, 107 – 119; h) E.
Scharrer, S. Chang, M. Brookhart, Organometallics 1995, 14,
5686 – 5694; i) M. Brookhart, B. E. Grant, J. Am. Chem. Soc.
1993, 115, 2151 – 2156; j) X.-L. Luo, R. H. Crabtree, J. Am.
Chem. Soc. 1989, 115, 2527 – 2535.
[4] For reviews: a) G. Nikonov, Adv. Organomet. Chem. 2005, 53,
217 – 309; b) J. Y. Corey, J. Braddock-Wilking, Chem. Rev. 1999,
99, 175 – 292; c) U. Schubert, Adv. Organomet. Chem. 1990, 30,
151 – 187; d) S. Lachaize, S. Sabo-Etienne, Eur. J. Inorg. Chem.
2006, 2115 – 2127; e) Z. Lin, Chem. Soc. Rev. 2002, 31, 239 – 245;
f) J. J. Schneider, Angew. Chem. 1996, 108, 1132 – 1139; Angew.
Chem. Int. Ed. Engl. 1996, 35, 1068 – 1075; g) R. H. Crabtree,
Angew. Chem. 1993, 105, 828 – 845; Angew. Chem. Int. Ed. Engl.
1993, 32, 789 – 805.
[5] Isolated cationic silane s-complexes with X-ray analysis:
a) S. T. N. Freeman, F. R. Lemke, L. Brammer, Organometallics
2002, 21, 2030 – 2032; isolated cationic silane s-complexes
without X-ray analysis: b) X. Fang, B. L. Scott, K. D. John,
G. J. Kubas, Organometallics 2000, 19, 4141 – 4149.
Figure 3. Relevant orbitals for interaction between the silane and
iridium.
[6] Calculations have identified complexes with minima showing
smaller Si–M interactions: a) C. M. Nagaraja, P. Parameswaran,
E. D. Jemmis, B. R. Jagirdar, J. Am. Chem. Soc. 2007, 129, 5587 –
5596; b) S. F. Vyboishchikov, G. I. Nikonov, Organometallics
2007, 26, 4160 – 4169; c) S. K. Ignatov, N. H. Rees, B. R. Tyrrell,
S. R. Duberley, A. G. Razuvaev, P. Mountford, G. I. Nikonov,
Chem. Eur. J. 2004, 10, 4991 – 4999; d) H. Rabaâ, J.-Y. Saillard,
U. Schubert, J. Organomet. Chem. 1987, 330, 397 – 413.
[7] A neutral Zr dimer with a linear Si-H-Zr interaction has been
observed in solid state but does not persist in solution: G.
Ciruelo, T. Cuenca, R. Gómez, R. Gomez-Sal, A. Martin, J.
Chem. Soc. Dalton Trans. 2001, 1657 – 1663.
populations are consistent with greater donation from s SiH
to s* IrC and greater back-donation from dp* Ir to s* SiH as
the silane coordination geometry changes from 4p, 4d, to 4d’.
In summary, we report structural, spectroscopic, and
computational characterization of a cationic h1-H(Si) silane
complex, 2. The d(1H) and JSi-H values for 2 fall into the range
observed for h2-SiH complexes, therefore these data alone do
not allow assignment of the h1-H(Si) coordination mode.
Computational studies indicate that the bulky substituents on
phosphorus in the POCOP ligand dictate the coordination
mode of the silane and in complexes with trimmed ligands h2-
SiH conformers are energy minima. The small energy differ-
ence between h1-H(Si) and h2-SiH conformers indicates that
backbonding from Ir to SiH s* in these cationic complexes is
not a very important stabilizing interaction.
[8] See Supporting Information for experimental details including
complete 1H, 31P and 29Si NMR characterization.
[9] a) I. Goettker-Schnetmann, M. Brookhart, J. Am. Chem. Soc.
2004, 126, 9330 – 9338; b) I. Goettker-Schnetmann, P. White, M.
Brookhart, J. Am. Chem. Soc. 2004, 126, 1804 – 1811; c) I.
Goettker-Schnetmann, P. White, M. Brookhart, Organometallics
2004, 23, 1766 – 1776.
Received: November 22, 2007
Revised: February 7, 2008
Published online: April 24, 2008
[10] Usually
JSi-H < 20 Hz for classical H-M-Si interactions, see
ref. [3]; JSi-H = 175 Hz for free Et3SiH.
[11] Crystallographic data for 2: C52H56BF20IrO2P2Si, Mr = 1386.01,
¯
collection temperature 100(2) K, triclinic, space group P1, a =
Keywords: s complexes · coordination mode ·
12.4133(7), b = 13.9005(8), c = 17.0525(9) Š, a = 70.938(2), b =
87.821(2), g = 88.840(2)8, V= 2779.0(3) Š3, Z = 2, R1 = 0.0246
[I > 2s(I)]. CCDC 676582 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
.
end-on coordination · iridium · silane complexes
[1] a) G. J. Kubas, Metal Dihydrogen and s-Bond Complexes,
Kluwer/Plenum, New York, 2001; b) J. E. Bercaw, J. A.
Labinger, Proc. Natl. Acad. Sci. USA 2007, 104, 6899 – 6900,
and the following articles in this special feature “Coordination
Chemistry of Saturated Molecules”.
[12] For example, Ir–Si 2.390(1) Š in [Cp’Ir(H)2(SiEt3)2]: J. S. Ricci,
T. F. Koetzle, M. J. Fernandez, P. M. Maitlis, J. C. Green, J.
Organomet. Chem. 1986, 299, 383 – 389.
[13] Gaussian 03, Revision D.02; B3LYP; LANL2DZ on Ir(+f
polarization); 6-311G** on other atoms. For details regarding
the DFT study, see Supporting Information.
[2] a) J. Yang, M. Brookhart, J. Am. Chem. Soc. 2007, 129, 12656 –
12657; b) M. D. Doherty, B. Grant, P. S. White, M. Brookhart,
Organometallics 2007, 26, 5950 – 5960.
[14] a) A. E. Reed, L. A. Curtiss, F. Weinhold, Chem. Rev. 1988, 88,
899 – 926; b) A. E. Reed, R. B. Weinstock, F. Weinhold, J. Chem.
Phys. 1985, 83, 735 – 746.
[3] a) R. N. Perutz, S. Sabo-Etienne,Angew. Chem. 2007, 119, 2630 –
2645; Angew. Chem. Int. Ed. 2007, 46, 2578 – 2592; b) S. L.
Matthews, V. Pons, D. M. Heinekey, Inorg. Chem. 2006, 45,
Angew. Chem. Int. Ed. 2008, 47, 4141 –4143
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
4143