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DOI: 10.1039/A701396E (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2937-2948

Reactions of [Ru5(µ5-C2PPh2) (µ-PPh2)(CO)13] with dimethyl disulfide. Synthesis of an open Ru5 cluster containing the dicarbon (C2) ligand and related chemistry

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Chris J. Adams, Michael I. Bruce, Brian W. Skelton and Allan H. White

Abstract

The reaction between [Ru5(µ5-C2PPh2)(µ- PPh2)(CO)13] and Me2S2 yielded [Ru5(µ5-C2PPh2)(µ- SMe)2(µ-PPh2)(CO)13] as the major product. When heated the latter yielded the dicarbon complexes [Ru5(µ5-C2)(µ-SMe)2( µ-PPh2)2(CO)12] and [Ru5(µ5-C2)(µ-SMe)2( µ-PPh2)2(CO)11]. In large-scale preparations of the latter four minor products were isolated: two isomers of [Ru5(µ5-C2PPh2)(µ- SMe)2(µ-PPh2)(CO)12], the tetranuclear complex [Ru4(µ4-C2PPh2)(µ- SMe)2(µ-PPh2)(CO)10] and [Ru5(µ5-C2)(µ-SMe)4( µ-PPh2)2(CO)10]. The latter is also formed by direct reaction of [Ru5(µ5-C2)(µ-SMe)2( µ-PPh2)2(CO)11] with Me2S2. All new complexes have been fully characterised by single-crystal X-ray studies. In the three Ru5(C2PPh2) complexes the C2PPh2 ligand acts as a seven-electron donor, whereas in the Ru4 complex it donates only five electrons to the cluster. In the C2 complexes, the different C–C separations [between 1.26(2) and 1.305(5) Å] suggest a variable degree of interaction with the metal core (electron donation and back-bonding), the ligand formally donating either six or four electrons to the cluster. This is borne out by the Ru–Ru separations, average values of which range between 2.791 and 2.916 Å. The conversion of [Ru5(µ5-C2PPh2)(µ- PPh2)(CO)13] into [Ru5(µ5-C2)(µ-SMe)2( µ-PPh2)2(CO)11] involves sequential formation of several of these complexes, which reactions are discussed.

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