Binuclear organometallic compounds VIII. Oxidative addition of Si-H or Si-Cl compounds to low valent Fe, Co, or Ni complexes stabilised by mono- or bi-dentate phosphines

Michael F. Lappert, G. Speier

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Abstract

The reactions of [(Ph3P)4Ni], [(Ph3P)3CoN2], [(dp)2Ni], [(dp)2CoH], [(dp)2Fe(C2H4)] or [(dp)2FeH2] (dp = Ph2PCH2CH2Ph2P) with PhnSiCl4-n (n = 1, 2, or 3), PhnSiH4-n, X3SiH (X = Cl or Et), or R2ClSiH (R = Ph or Me) have been investigated. Solid complexes were isolated which, for the most part, were insoluble in non-polar solvents. Assignments of structures are therefore incomplete, and are based on microanalysis, IR spectra, analogies with established reactions, and (in some cases) chemical degradation. Evidence is presented for the following: (i) for NiII, products from [(Ph3P)4Ni] and HSiXX′X″ (XX′X″ = Ph3, Ph2H or PhH2), the cyclic [(Ph3P)2NiSiCl2]2, and the five-coordinate [(dp)2-NiX]+[SiCl3]- (X = H or Cl3Si); (ii) for CoIII, the six-coordinate cis-octahedral [(dp)2CoH2]+ [SiXX′X″]- (XX′X″ = Cl3, Cl2Me, ClMe2, or ClPh2); and for FeII, the four-coordinate [(dp)FeH(SiCl3)] and the six-coordinate [(dp)2Fe(X)SiCl3] (X = H, Cl, or Cl3Si).

Original languageEnglish
Pages (from-to)329-339
Number of pages11
JournalJournal of Organometallic Chemistry
Volume80
Issue number3
DOIs
Publication statusPublished - Nov 5 1974

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Organometallic Compounds
Phosphines
organometallic compounds
Microanalysis
Organometallics
phosphines
Degradation
microanalysis
degradation
products

ASJC Scopus subject areas

  • Biochemistry
  • Chemical Engineering (miscellaneous)
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Science (miscellaneous)
  • Materials Chemistry

Cite this

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title = "Binuclear organometallic compounds VIII. Oxidative addition of Si-H or Si-Cl compounds to low valent Fe, Co, or Ni complexes stabilised by mono- or bi-dentate phosphines",
abstract = "The reactions of [(Ph3P)4Ni], [(Ph3P)3CoN2], [(dp)2Ni], [(dp)2CoH], [(dp)2Fe(C2H4)] or [(dp)2FeH2] (dp = Ph2PCH2CH2Ph2P) with PhnSiCl4-n (n = 1, 2, or 3), PhnSiH4-n, X3SiH (X = Cl or Et), or R2ClSiH (R = Ph or Me) have been investigated. Solid complexes were isolated which, for the most part, were insoluble in non-polar solvents. Assignments of structures are therefore incomplete, and are based on microanalysis, IR spectra, analogies with established reactions, and (in some cases) chemical degradation. Evidence is presented for the following: (i) for NiII, products from [(Ph3P)4Ni] and HSiXX′X″ (XX′X″ = Ph3, Ph2H or PhH2), the cyclic [(Ph3P)2NiSiCl2]2, and the five-coordinate [(dp)2-NiX]+[SiCl3]- (X = H or Cl3Si); (ii) for CoIII, the six-coordinate cis-octahedral [(dp)2CoH2]+ [SiXX′X″]- (XX′X″ = Cl3, Cl2Me, ClMe2, or ClPh2); and for FeII, the four-coordinate [(dp)FeH(SiCl3)] and the six-coordinate [(dp)2Fe(X)SiCl3] (X = H, Cl, or Cl3Si).",
author = "Lappert, {Michael F.} and G. Speier",
year = "1974",
month = "11",
day = "5",
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language = "English",
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pages = "329--339",
journal = "Journal of Organometallic Chemistry",
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T1 - Binuclear organometallic compounds VIII. Oxidative addition of Si-H or Si-Cl compounds to low valent Fe, Co, or Ni complexes stabilised by mono- or bi-dentate phosphines

AU - Lappert, Michael F.

AU - Speier, G.

PY - 1974/11/5

Y1 - 1974/11/5

N2 - The reactions of [(Ph3P)4Ni], [(Ph3P)3CoN2], [(dp)2Ni], [(dp)2CoH], [(dp)2Fe(C2H4)] or [(dp)2FeH2] (dp = Ph2PCH2CH2Ph2P) with PhnSiCl4-n (n = 1, 2, or 3), PhnSiH4-n, X3SiH (X = Cl or Et), or R2ClSiH (R = Ph or Me) have been investigated. Solid complexes were isolated which, for the most part, were insoluble in non-polar solvents. Assignments of structures are therefore incomplete, and are based on microanalysis, IR spectra, analogies with established reactions, and (in some cases) chemical degradation. Evidence is presented for the following: (i) for NiII, products from [(Ph3P)4Ni] and HSiXX′X″ (XX′X″ = Ph3, Ph2H or PhH2), the cyclic [(Ph3P)2NiSiCl2]2, and the five-coordinate [(dp)2-NiX]+[SiCl3]- (X = H or Cl3Si); (ii) for CoIII, the six-coordinate cis-octahedral [(dp)2CoH2]+ [SiXX′X″]- (XX′X″ = Cl3, Cl2Me, ClMe2, or ClPh2); and for FeII, the four-coordinate [(dp)FeH(SiCl3)] and the six-coordinate [(dp)2Fe(X)SiCl3] (X = H, Cl, or Cl3Si).

AB - The reactions of [(Ph3P)4Ni], [(Ph3P)3CoN2], [(dp)2Ni], [(dp)2CoH], [(dp)2Fe(C2H4)] or [(dp)2FeH2] (dp = Ph2PCH2CH2Ph2P) with PhnSiCl4-n (n = 1, 2, or 3), PhnSiH4-n, X3SiH (X = Cl or Et), or R2ClSiH (R = Ph or Me) have been investigated. Solid complexes were isolated which, for the most part, were insoluble in non-polar solvents. Assignments of structures are therefore incomplete, and are based on microanalysis, IR spectra, analogies with established reactions, and (in some cases) chemical degradation. Evidence is presented for the following: (i) for NiII, products from [(Ph3P)4Ni] and HSiXX′X″ (XX′X″ = Ph3, Ph2H or PhH2), the cyclic [(Ph3P)2NiSiCl2]2, and the five-coordinate [(dp)2-NiX]+[SiCl3]- (X = H or Cl3Si); (ii) for CoIII, the six-coordinate cis-octahedral [(dp)2CoH2]+ [SiXX′X″]- (XX′X″ = Cl3, Cl2Me, ClMe2, or ClPh2); and for FeII, the four-coordinate [(dp)FeH(SiCl3)] and the six-coordinate [(dp)2Fe(X)SiCl3] (X = H, Cl, or Cl3Si).

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