Reactions of tetranuclear rhodium-triruthenium clusters with di- and tri-phosphines and with alkynes

Jean L. Le Grand, W. Edward Lindsell, Kevin J. McCullough, Calum H. McIntosh, A. Gavin Meiklejohn

Research output: Contribution to journalArticle

Abstract

The compound [RhRu3(µ-H)2(µ-CO)(CO)9(cp)] 1 (cp = ?5-C2H5) and an equimolar amount of diphosphine Ph2P(CH2)nPPh2 [n = 1 (dppm), 2 (dppe) or 3 (dppp)] react at ambient temperature principally with cleavage of the heteronuclear cluster to form several homonuclear rhodium and ruthenium products. Isolated ruthenium clusters are simple phosphine derivatives of [Ru3(CO)12] or [Ru4(µ-H)4(CO)12], including [Ru3(µ-diphos)2(CO)8] (diphos = dppm or dppe), [Ru3(µ-diphos)(CO)10] and [{Ru3(µ-diphos)(CO)9}2(µ-diphos)] (diphos = dppe or dppp), and [Ru4(µ-H)4(CO)10(dppp)]. Reaction of 1 with the triphosphine MeC(CH2PPh2)3 affords hydrido-clusters [Ru3(µ-H)H(µ-triphos)(CO)8] and [Ru3(µ-H){µ-PPhCH2CMe(CH2PPh 2)2(CO)8] 12, the latter formed by elimination of benzene under very mild reaction conditions. The solid-state structure of cluster 12 has been determined by X-ray crystallographic analysis [monosolvate with dichloromethane, monoclinic, space group P21/n, a = 19.549(3), b = 14.2462(21), c = 16.429(4) Å, ß = 90.271(18)°, Z = 4, R = 0.051, R' = 0.060] and the geometrical non-rigidity of this asymmetric molecule in solution is revealed by variable-temperature 31P NMR spectroscopy. Reactions of cluster 1 with alkynes, RC=CR (R = Ph or Et), give heteronuclear products, including isomers of [RhRu3(C2R2)(CO)9(cp)] and trimetallic clusters [RhRu2(C2R2)(CO)n(cp)] (R = Et, n = 7; R = Ph, n = 8); from reaction of [RhRu3(µ-H)4(CO)9(?5-C 5Me5)] with PhC=CPh a related tetranuclear cluster [RhRu3(C2R2)(CO)9(? 5-C5Me5)] is formed. A new, octahedral heteronuclear cluster [Rh2Ru4(µ-H)2(CO)12(cp) 2] is also reported.

Original languageEnglish
Pages (from-to)1089-1099
Number of pages11
JournalJournal of the Chemical Society, Dalton Transactions
Issue number6
DOIs
Publication statusPublished - 1992

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