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Organometallics
Volumn 26, Issue 23, 2007, Pages 5468-5472
Synthesis of a cobalt - Phospholyl half-sandwich complex and its transformation into a phosphacobaltocene
Author keywords

[No Author keywords available]
Indexed keywords

ACETYLATION; COMPLEXATION; CRYSTAL STRUCTURE; LITHIUM COMPOUNDS; LOW TEMPERATURE OPERATIONS; SYNTHESIS (CHEMICAL);
EID: 36249017503     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om0610952     Document Type: Article
Times cited : (12)
References (77)
  • 9
    • 33646424358 scopus 로고    scopus 로고
    • For rather different reactions involving thermolysis of phospholes, see also: Bitta, J.; Fassbender, S.; Reiss, G.; Ganter, C. Organometallics 2006, 25, 2394-2397, and references therein.
    • For rather different reactions involving thermolysis of phospholes, see also: Bitta, J.; Fassbender, S.; Reiss, G.; Ganter, C. Organometallics 2006, 25, 2394-2397, and references therein.
  • 10
    • 36248997383 scopus 로고    scopus 로고
    • Phospholyl ligands are more electron-withdrawing than their cyclopentadienyl analogues when coordinated to soft metal centers, so that loss of CO ligands is facilitated.46,47
    • 46,47
  • 11
    • 36248931260 scopus 로고    scopus 로고
    • Neutral precursors such as [Co(η5-phospholyl)(CO) 2]47 and [Mn-(η5-phospholyl)(CO) 3]63 have been shown to undergo useful displacement reactions with neutral ligands. Also for for the middle transition elements see: [M(η5-phospholyl)(CO)2X, M, Mo64 or W,65 X, TMSn, I
    • 65 X = TMSn, I).
  • 36
    • 36249004128 scopus 로고    scopus 로고
    • There is evidence that the synthesis of unhindered phosphametallocenes containing the late transition metals is problematical, 52,66 so unhindered complexes were not envisioned at this stage
    • 52,66 so unhindered complexes were not envisioned at this stage.
  • 38
    • 36248942787 scopus 로고    scopus 로고
    • The most frequently used and reliable synthesis of this kind of complex involves oxidation and high-temperature pyrolysis steps, which are not necessarily compatible with functionalized cyclopentadienyl ligands.1 Furthermore, nonhindered 1,1′-diphosphaplumbocenes are prone to reductive elimination of the corresponding 1,1′-biphospholes.34
    • 34
  • 55
    • 0012557011 scopus 로고    scopus 로고
    • Obviously, the compound is also a surrogate of [Co(Cp)X] species (X = halogen, Cp cyclopentadienyl or derivative), which have also found extensive uses including, for example, in the synthesis of cobalt complexes with unusual spin states: Brunker, T. J.; Cowley, A. R.; O'Hare, D. Organometallics 2002, 21, 3123-3138
    • Obviously, the compound is also a surrogate of [Co(Cp)X] species (X = halogen, Cp cyclopentadienyl or derivative), which have also found extensive uses including, for example, in the synthesis of cobalt complexes with unusual spin states: Brunker, T. J.; Cowley, A. R.; O'Hare, D. Organometallics 2002, 21, 3123-3138
  • 56
    • 0031764229 scopus 로고    scopus 로고
    • and poly(π-complexes): Schneider, J. J.; Wolf, D.; Janiak, C.; Heinemann, O.; Rust, J.; Krüger, C. Chem.-Eur. J. 1998, 4, 1982-1991.
    • and poly(π-complexes): Schneider, J. J.; Wolf, D.; Janiak, C.; Heinemann, O.; Rust, J.; Krüger, C. Chem.-Eur. J. 1998, 4, 1982-1991.
  • 57
    • 36249022939 scopus 로고    scopus 로고
    • For crystallographically proven examples see, for example, refs 67 and 68. The instability of unencumbered electron-excessive paramagnetic phospholyl complexes results principally from the possibility of reducing metal electron count through an η5 to η1 ring slip of the phospholyl ligand, whereby the ligand anion goes from being a formal 6e donor in a monomelic metallocene to a 4e donor in a μ2- η2(P)-bridged dimer.66,69 The dimeric complex can then attain a diamagnetic closed-shell configuration directly (if the precursor is a formal 20 VE phosphametallocene) or through the formation of a metal-metal bond if 19 VE, In such cases, the effect of the hindrance is to sterically disfavor the phospholyl bridging position and thereby confer a relative stabilization upon the electron-excessive phosphametallocene. 69 It is not clear how such a reduction in the number of electrons made available to a m
    • 71 halides.
  • 59
    • 36248996167 scopus 로고    scopus 로고
    • Cloke, F. G. N, Green, J. C, Hanks, J. R, Nixon, J. F, Suter, J. L. J. Chem. Soc, Dalton Trans. 2000, 3534-3536. Bruce and Rocha have subsequently presented a very similar analysis, see ref 72
    • Cloke, F. G. N.; Green, J. C.; Hanks, J. R.; Nixon, J. F.; Suter, J. L. J. Chem. Soc., Dalton Trans. 2000, 3534-3536. Bruce and Rocha have subsequently presented a very similar analysis, see ref 72.
  • 63
    • 0037416021 scopus 로고    scopus 로고
    • In addition to the more classical uses illustrated by refs 12-26, this kind of ligand may also show interesting redox-driven properties; see: Gudat, D, Lewall, B, Nieger, M, Detmer, I, Szarvas, L, Saarenketo, P, Marconi, G. Chem.-Eur. J. 2003, 9, 661-670
    • In addition to the more classical uses illustrated by refs 12-26, this kind of ligand may also show interesting redox-driven properties; see: Gudat, D.; Lewall, B.; Nieger, M.; Detmer, I.; Szarvas, L.; Saarenketo, P.; Marconi, G. Chem.-Eur. J. 2003, 9, 661-670.

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.