Syntheses, structures and chemistry of the high-nuclearity ruthenium hydrido cluster anions [Ru10H2(CO)25]2- and [Ru11H(CO)27]3-

Philip J. Bailey, Michael A. Beswick, Brian F.G. Johnson, Jack Lewis, Mary McPartlin, Paul R. Raithby, M. Carmen Ramirez De Arellano

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Abstract

Thermolysis of [Ru3(CO)12] in ethanol yielded the decanuclear hydridoruthenium cluster dianion [Ru10H2(CO)25]2- 1. When a mixture of methanol and water is employed as thermolysis solvent the undecaruthenium hydridoruthenium trianion [Ru11H(CO)27]3- 2 is also formed. Crystal structure analysis of 1 as its [N(PPh3)2]+ salt and 2 as its [NEt3(CH2Ph)]+ salt showed their metal core structures to be related, 2 being a square-faced capped congener of 1. Cluster 2 was alternatively formed in near-quantitative yields when [Ru3(CO)12] was thermolysed in acetonitrile containing traces of water for several days. It was not possible to locate the hydride ligands in the structures by potential-energy-minimisation calculations, but strong signals were seen in the 1H NMR spectra at δ - 14.2 (s, 2 H) for 1 and at -5.47 (s, 1 H) for 2. On treatment of 1 and 2 with [Au(PPh3)Cl] in the presence of TlPF6, 1 showed no reactivity, but 2 reacted smoothly adding one [Au(PPh3)]+ moiety and giving a product characterised as [Ru11H(CO)27{Au(PPh3)}]2- 3. The structural relationships between the known high-nuclearity ruthenium hydrido carbonyl clusters are discussed, and their implications for a possible cluster build-up sequence considered.

Original languageEnglish
Pages (from-to)3515-3520
Number of pages6
JournalJournal of the Chemical Society - Dalton Transactions
Volume1996
Issue number17
DOIs
Publication statusPublished - 7 Sep 1996

ASJC Scopus subject areas

  • Chemistry(all)

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