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IV intermediates; see for example: M. Ohff, A. Ohff, M. E. van der Boom, D. Milstein, J. Am. Chem. Soc. 1997, 119, 11687.
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2
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0000326049
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Shilov-type alkane oxidation involves Pt(IV) intermediates: J. E. Bercaw, J. A. Labinger, S. Stahl, Angew. Chem. 1998, 110, 2298; Angew. Chem. Int. Ed. 1998, 37, 2180.
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Bercaw, J.E.1
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0031678723
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Shilov-type alkane oxidation involves Pt(IV) intermediates: J. E. Bercaw, J. A. Labinger, S. Stahl, Angew. Chem. 1998, 110, 2298; Angew. Chem. Int. Ed. 1998, 37, 2180.
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P. M. Maitlis, C. M. Spencer, B. E. Mann, J. Ruiz, P. O. Bentz, J. Chem. Soc. Chem. Commun. 1985, 1985.
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17
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3342954064
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see also ref. [11]
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Bergman et al. discussed a similar mechanistic controversy in C-H activation reactions mediated by cationic Ir complexes: P. Burger, R. G. Bergman, J. Am. Chem. Soc. 1993, 115, 10462; see also ref. [11].
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0039402875
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C. P. Lenges, P. S. White, M. Brookhart, Angew. Chem. 1999, 111, 535; Angew. Chem. Int. Ed. 1999, 38, 552.
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0031069002
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23
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1642639599
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-
note
-
5), - 16.0 (s, 2H, Co-H), and triplet and quartet signals diagnostic of a (silyl)ethyl group. For 3, see Experimental Section.
-
-
-
-
24
-
-
1642639598
-
-
note
-
2 is not observed, and complex 3 is generated instead. Complex 3 is not significantly active in catalytic hydrosilylation of aromatic ketones.
-
-
-
-
25
-
-
1642592984
-
-
unpublished results
-
3 as substrate; however, this type of intermediate was observed in a reaction with 1b: C. P. Lenges, M. Brookhart, unpublished results.
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-
-
Lenges, C.P.1
Brookhart, M.2
-
26
-
-
1642639596
-
-
note
-
6]benzene result in selective deuteration of the α-position of vinyltrimethylsilane; see ref. [16];
-
-
-
-
27
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-
0000314931
-
-
b) the formation of silylenes by α-elimination from silyl hydrides has been discussed, and examples of this reactive species have recently been isolated: G. P Mitchell, T. D. Tilley, Angew. Chem. 1998, 110, 2602; Angew. Chem. Int. Ed. 1998, 37, 2524.
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Angew. Chem.
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Mitchell, G.P.1
Tilley, T.D.2
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28
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0032476165
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b) the formation of silylenes by α-elimination from silyl hydrides has been discussed, and examples of this reactive species have recently been isolated: G. P Mitchell, T. D. Tilley, Angew. Chem. 1998, 110, 2602; Angew. Chem. Int. Ed. 1998, 37, 2524.
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Angew. Chem. Int. Ed.
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-
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29
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0000675582
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2(dmso)] to generate a rhodium(V) intermediate: M. Gomez, J. M. Kisenyi, G. J. Sunley, P. M. Maitlis, J. Organomet. Chem. 1985, 296, 197.
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Gomez, M.1
Kisenyi, J.M.2
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Maitlis, P.M.4
-
30
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1642608525
-
-
note
-
The geometries of the four independent molecules of 3 in the unit cell show very similar values for the Co-Si distances. However, small deviations between 2.25 A (Co Sil) and 2.26 A (Co-Si2) are observed within each molecule in the unit cell.
-
-
-
-
31
-
-
1642592983
-
-
note
-
3 group in the Rh complex elongates the Rh-Si bond distance increasing the expected difference between Rh Si and Co-Si (see Table 1).
-
-
-
-
33
-
-
1642624012
-
-
note
-
For calculations of energies and gradients we used the hybrid nonlocal density functional according to Becke and Lee, Yang, and Parr (B3LYP). For all calculations the program Gaussian94 was used with the fine integration grid option. For geometry optimization a gradient convergence criterion of 0.1 E - 6 was used. For C. H. and Si we used the 6-31G* split-valence basis set supplied by the program. For Co we used an effective core potential basis set according to Hay and Wadt with double zeta quality in the valence region.
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-
-
34
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0345491105
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C. Lee, W. Yang, R. G. Parr, Phys. Rev. Sect. B 1988, 37, 785.
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Phys. Rev. Sect. B
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Lee, C.1
Yang, W.2
Parr, R.G.3
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36
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0004133516
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Gaussian, Inc., Carnegie Office Park, Building 6, Pittsburgh, PA 15106, USA
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Gaussian 94. Revision E.2. Gaussian, Inc., Carnegie Office Park, Building 6, Pittsburgh, PA 15106, USA, 1995
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(1995)
Gaussian 94. Revision E.2
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41
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1642639597
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note
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1-orbital into a Si p, orbital (about 2% of the σ bond) also contributes to the Co-Si bond. Some contribution to the stability of the complex appears to arise from the overlap population of Si and the hydrido ligands of 0.1 electrons.
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42
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0039331562
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K. J. Klabunde, Z. Yao, A. C. Hupton, Inorg. Chim. Acta 1997, 259, 119.
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Inorg. Chim. Acta
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Klabunde, K.J.1
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Hupton, A.C.3
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43
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0028478558
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P. I. Djurovich, P. J. Carroll, D. H. Berry, Organometallics 1994, 13, 2551.
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(1994)
Organometallics
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Djurovich, P.I.1
Carroll, P.J.2
Berry, D.H.3
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