메뉴 건너뛰기




Volumn 39, Issue 9, 2000, Pages 1676-1679

High oxidation state organocobalt complexes: Synthesis and characterization of dihydridodisilyl cobalt(V) species

Author keywords

Cobalt; Density functional calculations; Hydrido complexes; Si H activation; Silanes

Indexed keywords

COBALT COMPLEX; COBALT DERIVATIVE; SILANE DERIVATIVE;

EID: 0034595410     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(20000502)39:9<1676::AID-ANIE1676>3.0.CO;2-M     Document Type: Article
Times cited : (58)

References (43)
  • 2
    • 0000326049 scopus 로고    scopus 로고
    • 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.
    • (1998) Angew. Chem. , vol.110 , pp. 2298
    • Bercaw, J.E.1    Labinger, J.A.2    Stahl, S.3
  • 3
    • 0031678723 scopus 로고    scopus 로고
    • 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.
    • (1998) Angew. Chem. Int. Ed. , vol.37 , pp. 2180
  • 17
    • 3342954064 scopus 로고
    • see also ref. [11]
    • 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].
    • (1993) J. Am. Chem. Soc. , vol.115 , pp. 10462
    • Burger, P.1    Bergman, R.G.2
  • 20
    • 0033557427 scopus 로고    scopus 로고
    • C. P. Lenges, P. S. White, M. Brookhart, Angew. Chem. 1999, 111, 535; Angew. Chem. Int. Ed. 1999, 38, 552.
    • (1999) Angew. Chem. Int. Ed. , vol.38 , pp. 552
  • 23
    • 1642639599 scopus 로고    scopus 로고
    • 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 scopus 로고    scopus 로고
    • 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 scopus 로고    scopus 로고
    • unpublished results
    • 3 as substrate; however, this type of intermediate was observed in a reaction with 1b: C. P. Lenges, M. Brookhart, unpublished results.
    • Lenges, C.P.1    Brookhart, M.2
  • 26
    • 1642639596 scopus 로고    scopus 로고
    • note
    • 6]benzene result in selective deuteration of the α-position of vinyltrimethylsilane; see ref. [16];
  • 27
    • 0000314931 scopus 로고    scopus 로고
    • 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.
    • (1998) Angew. Chem. , vol.110 , pp. 2602
    • Mitchell, G.P.1    Tilley, T.D.2
  • 28
    • 0032476165 scopus 로고    scopus 로고
    • 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.
    • (1998) Angew. Chem. Int. Ed. , vol.37 , pp. 2524
  • 30
    • 1642608525 scopus 로고    scopus 로고
    • 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 scopus 로고    scopus 로고
    • 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 scopus 로고    scopus 로고
    • 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.
  • 36
    • 0004133516 scopus 로고
    • Gaussian, Inc., Carnegie Office Park, Building 6, Pittsburgh, PA 15106, USA
    • Gaussian 94. Revision E.2. Gaussian, Inc., Carnegie Office Park, Building 6, Pittsburgh, PA 15106, USA, 1995
    • (1995) Gaussian 94. Revision E.2
  • 41
    • 1642639597 scopus 로고    scopus 로고
    • note
    • 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.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.