A new family of phosphido-bridged dinuclear ruthenium carbonyl complexes: Synthesis of [Ru2(CO)6{μ-P(C(CH)3O)2} (μ-η12-C(CH)3O)] and its reactivity towards terminal alkynes

Wai Yeung Wong, F. L. Ting, W. L. Lam

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Abstract

Thermal reaction of [Ru3(CO)12] with tri(2-furyl)phosphine affords the dinuclear phosphido-bridged complex [Ru2(CO)6{μ-P(C(CH)3O)2} (μ-η1,η2-C(CH)3O)] 1a in good yield via cleavage of Ru-Ru and P-C(furyl) bonds in the starting compounds and a small amount of the disubstitution product [Ru3(CO)10{P(C(CH)3O)3} 2] 1b. The X-ray structural analysis of 1a shows that it contains a dissociated furyl fragment bonded to the Ru2 unit in a μ-η1,η2 coordination mode through one σ and one π bond. This represents the first structurally characterised example of such a furyl-bonded dinuclear organometallic complex. Complex 1a readily reacts with two equivalents of terminal alkynes HC≡CR [R = Ph, p-C6H4Me, p-C6H4NO2, (C4H2S)C≡CH or (C4H2S)2C≡CH] by an interesting head-to-tail ynyl coupling with a furan group to form a series of phosphido-bridged diruthenium compounds containing a novel furyl-substituted C4 hydrocarbyl chain of stoichiometry [Ru2(CO)4{μ-P(C(CH)3O)2} {μ-η1,η1,η2,η 3-RCC(H)C(R)C(H)-C(CH)3O}] [R = Ph 2, p-C6H4Me 3, p-C6H4NO2 4, (C4H2S)C≡CH 5 or (C4H2S)2C≡CH 6] in moderate to good yields, all of which have been characterised by spectroscopic and crystallographic methods. Assignments of the proton NMR spectra have been made with the aid of a 2-D 1H-1H COSY technique. On reaction with the thienyl-linked diyne ligands, only one free C≡CH group is involved in the coupling sequence while the other terminal alkyne functionality remains intact. All these new dinuclear complexes are electron precise with 34 cluster valence electrons.
Original languageEnglish
Pages (from-to)2981-2988
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number20
Publication statusPublished - 20 Nov 2001
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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