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On the Reaction of C(PPh3

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On the Reaction of C(PPh

3

)

2

with [Co

2

(CO)

8

]: Formation and Structure of an Unusual Tetranuclear Cluster

Wolfgang Petz, Kirstin Wenck, and Bernhard Neum¨uller

Fachbereich Chemie der Philipps-Universit¨at Marburg, Hans Meerwein-Straße, 35032 Marburg, Germany

Reprint requests to Prof. W. Petz. E-mail: petz@staff.uni-marburg.de or Prof. B. Neum¨uller. E-mail: neumuell@chemie.uni-marburg.de Z. Naturforsch.2007,62b,413 – 418; received December 3, 2006

Dedicated to Prof. Helgard G. Raubenheimer on the occasion of his 65thbirthday

The reaction of the carbodiphosphorane C(PPh3)2(1) with [Co2(CO)8] results in the formation of the salt-like complex (HC{PPh3}2)[Co(CO)4] (2) in high yield if THF is used as the solvent. The proton of the cation stems from THF degradation. When the reaction is carried out in toluene, the tetranuclear cluster [Co4(CO)10(PPh3)(µ4-CCPPh3)] (3) is formed in low yield as the only complex which could be identified by X-ray analysis. The solvate3·C7H8crystallizes in the triclinic space groupP¯1 witha= 1040.8(2),b= 1387.4(2),c= 1923.0(2) pm,α = 71.96(1),β = 88.69(1),γ= 71.46(1),Z= 2. The structure of the cluster with 64 CVE is that of a “spiked triangle” in which the triphenylphosphonioacetylide CCPPh3acts as a six-electron donor and the bonding mode is that of a µ42coordination.

Key words:Tetranuclear Cobalt Cluster, Carbodiphosphorane, Phosphacumulene Ligand, Proton Abstraction, Crystal Structure

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