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DOI: 10.1039/A605529J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 371-376

Reaction of a dicarbon Ru5 cluster with CO: crystal structures of [Ru5(µ4-C2)(µ-SMe)2( µ-PPh2)2(CO)13] and [Ru4(µ4-C2)(µ-SMe)2( µ-PPh2)2(CO)10]

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Chris J. Adams, Michael I. Bruce, Brian W. Skelton, Allan H. White, Gilles Frapper and Jean-François Halet

Abstract

The reaction between [Ru5(µ5-C2)(µ-SMe)2( µ-PPh2)2(CO)11] 1 and CO (30 atm) yielded [Ru5(µ4-C2)(µ-SMe)2( µ-PPh2)2(CO)13] 2 and [Ru4(µ4-C2)(µ-SMe)2( µ-PPh2)2(CO)10] 3, both characterised by single-crystal X-ray crystallography. In 2, addition of 2[hair space]CO results in the net cleavage of two Ru–Ru bonds and expansion of the resulting Ru3 cluster. The C2 ligand bridges one edge of the Ru3 core and the isolated Ru–Ru bonded fragment in a µ,µ-η1,η2 mode, albeit with asymmetric Ru–C2 π interactions. In 3, one Ru atom has been excised from the cluster present in 1. One Ru–Ru bond is bridged by two SMe groups as a result of migration of one of these. Although the C2 ligand bridges all four metal atoms, only two Ru[thin space (1/6-em)]–[thin space (1/6-em)]Ru bonds are present, with the non-bonded Ru[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]Ru vector being bridged by PPh2. Extended-Hückel molecular orbital calculations have been used to rationalise the observed structures.

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