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Related bis(diaminocarbene)palladium complexes are known: a) P. L. Arnold, F. G. N. Cloke, T. Geldbach, P. B. Hitchcock, Organometallics 1999, 18, 3228;
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9744248685
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39
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34247242755
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2Pd] with 1 in a ration of more than 2:1 gave an interesting dinuclear palladium complex with a bridging dialkylsilylene ligand. For details, see: C. Watanabe, T. Iwamoto, C. Kabuto, M. Kira, Chem. Lett. 2007, 36, 284.
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2Pd] with 1 in a ration of more than 2:1 gave an interesting dinuclear palladium complex with a bridging dialkylsilylene ligand. For details, see: C. Watanabe, T. Iwamoto, C. Kabuto, M. Kira, Chem. Lett. 2007, 36, 284.
-
-
-
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40
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53549129809
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[4c] A related tris(dialkylsilylene)palladium complex does not form even when bis(tricyclohexylphosphine)palladium is treated with an excess amount of 1, probably due to steric reasons.
-
[4c] A related tris(dialkylsilylene)palladium complex does not form even when bis(tricyclohexylphosphine)palladium is treated with an excess amount of 1, probably due to steric reasons.
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41
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0032483737
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For donor-free neutral silylene complexes, see: a
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53549103660
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CCDC 624745 (2) and 624747 (3) contain the supplementary crystallographic 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.
-
CCDC 624745 (2) and 624747 (3) contain the supplementary crystallographic 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.
-
-
-
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50
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53549127910
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The van der Waals radii of palladium and methyl are taken to be 1.63 and 2.00 Å, respectively: a L. Pauling, The Nature of the Chemical Bond, 3rd ed.; Cornell University Press, New York, 1960, p. 261;
-
The van der Waals radii of palladium and methyl are taken to be 1.63 and 2.00 Å, respectively: a) L. Pauling, The Nature of the Chemical Bond, 3rd ed.; Cornell University Press, New York, 1960, p. 261;
-
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52
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53549102014
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2) has an N-Ni-N angle of 167.9(1)°: R. A. Bartlett, H. Chen, P. P. Power, Angew. Chem. 1989, 101, 325;
-
2) has an N-Ni-N angle of 167.9(1)°: R. A. Bartlett, H. Chen, P. P. Power, Angew. Chem. 1989, 101, 325;
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54
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0001229065
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53549135570
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[8a] A plausible mechanism for the hydrogenation of 2 is proposed in the Supporting Information.
-
[8a] A plausible mechanism for the hydrogenation of 2 is proposed in the Supporting Information.
-
-
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57
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33746063699
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2] (δ = 33.5 ppm; dcpe = 1,2-bis(dicyclohexylphosphino)-ethane): R. C. Boyle, D. Pool, H. Jacobsen, M. J. Fink, J. Am. Chem. Soc. 2006, 128, 9054.
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2] (δ = 33.5 ppm; dcpe = 1,2-bis(dicyclohexylphosphino)-ethane): R. C. Boyle, D. Pool, H. Jacobsen, M. J. Fink, J. Am. Chem. Soc. 2006, 128, 9054.
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53549135028
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The basis sets used were 6-31G* for Si, C, N, and H and Lanl2dz for Pd. See the Supporting Information for details of the calculations.
-
The basis sets used were 6-31G* for Si, C, N, and H and Lanl2dz for Pd. See the Supporting Information for details of the calculations.
-
-
-
-
68
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53549102306
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-1 for 5, 6, and 7, respectively.
-
-1 for 5, 6, and 7, respectively.
-
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69
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0002970819
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The low-lying vacant π orbital of silylene is indispensable for effective π back donation; the Si-Pd-Si angles in the optimized structures of palladium complexes 8 and 9, which have rather higher vacant pπ orbitals due to the donation of the nitrogen lone-pair electrons, are 153.2° and 180.0°, respectively. Previous theoretical studies using a different density functional method have also shown that 9 and other bis(carbene)palladium complexes adopt similar linear skeletal geometries: J. C. Green, R. G. Scurr, P. L. Arnold, F. G. N. Cloke, Chem. Commun. 1997, 1963;
-
The low-lying vacant π orbital of silylene is indispensable for effective π back donation; the Si-Pd-Si angles in the optimized structures of palladium complexes 8 and 9, which have rather higher vacant pπ orbitals due to the donation of the nitrogen lone-pair electrons, are 153.2° and 180.0°, respectively. Previous theoretical studies using a different density functional method have also shown that 9 and other bis(carbene)palladium complexes adopt similar linear skeletal geometries: J. C. Green, R. G. Scurr, P. L. Arnold, F. G. N. Cloke, Chem. Commun. 1997, 1963;
-
-
-
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70
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53549116558
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[23]
-
[23]
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-
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71
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53549126426
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See the Supporting Information for a qualitative explanation of the bent geometry as well as the significant agostic interaction in 12-electron dicoordinate metal complexes using the Walsh diagram
-
See the Supporting Information for a qualitative explanation of the bent geometry as well as the significant agostic interaction in 12-electron dicoordinate metal complexes using the Walsh diagram.
-
-
-
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