Role of the Reversible Opening of a Metal-Metal Bond in a Cluster-Assisted Transformation of Bis(diphenylphosphino)methane

NoëL Lugan, Jean Jacques Bonnet*, James A Ibers

*Corresponding author for this work

Research output: Contribution to journalArticle

33 Scopus citations

Abstract

A reinvestigation of the reaction of Ru3(CO)933-P(C6H5)CH2P(C6H5)(C6H4)) (2) with carbon monoxide (Lugan, N.; Bonnet, J.-J.; Ibers, J. A. J. Am. Chem. Soc. 1985, 107, 4484–4491) under milder conditions shows that at room temperature 2 is in equilibrium with the adduct Ru3(CO)1033-P(C6H5)CH2P-(C6H6)(C6H4)) (3a), in which one Ru-Ru bond has been broken. 3a has been isolated in 82% yield upon crystallization at -30 °C under a CO atmosphere. Similarly, 2 reacts at 0 °C with phosphines to afford compounds of general formula Ru3(CO)9L(μ33-P(C6H5)CH2P(C6H5)(C6H4)) (3b, L = P(C6H5)3; 3c, L = dppm). Addition of triphenylphosphine to compound 2 at 25 °C or warming a solution of 3a gives, among several compounds that have not been identified, the new dinuclear complex Ru2(CO)6(μ-η3-P(C6H6)-CH2P(C6H5)(C6H4)) (5). The nature of compounds 3a, 3b 3c, and 5 has been established by spectroscopic means and for compound 3a, 3c, and 5 by X-ray diffraction methods. Crystal data: 3a, triclinic, C1i—PI, Z = 2, a = 13.435 (2) Å, b = 14.039 (2) Å, c = 9.839 (2) Å, α = 92.50 (1)°, β= 113.94 (1)°, γ= 92.86 (1)° (t = -165 °C), final R(F) = 1.9%, NO = 5277, NV = 424; 3c, monoclinic, C52h—P21/c, Z = 4, a = 14.368 (2) Å, b = 25.612 (2) Å, c = 15.913 (2) Å, β= 108.09 (1)° (t = -150 °C), final R(F) = 6.8%, NO = 6301, NV = 412; 5, monoclinic, P21/c, Z = 4, a = 13.625 (3) Å, b = 9.951 (2) Å, c = 18.917 (4) Å, β = 97.46 (2)° (t = -155 °C), final R(F2) = 4.8%, NO = 4404, NV = 316.

Original languageEnglish (US)
Pages (from-to)1538-1545
Number of pages8
JournalOrganometallics
Volume7
Issue number7
DOIs
StatePublished - Jan 1 1988

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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