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Volumn 47, Issue 29, 2008, Pages 5386-5389

Fourteen-electron bis(dialkylsilylene)palladium and twelve-electron bis(dialkylsilyl)palladium complexes

Author keywords

Agostic interactions; Heterometallic complexes; Hydrogenation; Palladium; Silicon

Indexed keywords

ELECTRONS; GOLD COMPOUNDS; HYDROGEN; PALLADIUM; SILANES; SILICON;

EID: 53549126646     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200705954     Document Type: Article
Times cited : (42)

References (71)
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    • For reviews of silylene-containing transition-metal complexes, see: a, Eds, S. Patai, Z. Rappoport, Wiley, New York, Chapter 24;
    • For reviews of silylene-containing transition-metal complexes, see: a) T. D. Tilley in The Chemistry of Organic Silicon Compounds (Eds.: S. Patai, Z. Rappoport), Wiley, New York, 1989, Chapter 24;
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    • For pioneering works concerning donor-stabilized bis-(silylene)complexes, see: a
    • For pioneering works concerning donor-stabilized bis-(silylene)complexes, see: a) K. Ueno, H. Tobita, M. Shimoi, H. Ogino, J. Am. Chem. Soc. 1988, 110, 4092;
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    • H. Tobita, H. Kurita, H. Ogino, Organometallics 1998, 17, 2844. See also refs. [1c] and [1d].
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    • For recent reviews on 1 and related germylenes and stannylenes, see: a M. Kira, S. Ishida, T. Iwamoto, Chem. Rec. 2004, 4, 243;
    • For recent reviews on 1 and related germylenes and stannylenes, see: a) M. Kira, S. Ishida, T. Iwamoto, Chem. Rec. 2004, 4, 243;
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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;
    • 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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    • For recent reviews of transition-metal complexes of stable carbenes, see: e
    • For recent reviews of transition-metal complexes of stable carbenes, see: e) C. M. Crudden, D. P. Allen, Coord. Chem. Rev. 2004, 248, 2247;
    • (2004) Coord. Chem. Rev , vol.248 , pp. 2247
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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.
    • 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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    • [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.
  • 49
    • 53549103660 scopus 로고    scopus 로고
    • 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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    • 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;
  • 52
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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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    • [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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    • 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.
    • 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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    • and references therein
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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
    • 53549102306 scopus 로고    scopus 로고
    • -1 for 5, 6, and 7, respectively.
    • -1 for 5, 6, and 7, respectively.
  • 69
    • 0002970819 scopus 로고    scopus 로고
    • 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;
  • 70
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    • [23]
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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.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.