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Pincer ligand coordination at Co3 and Ru6 clusters: Syntheses, reactivity studies, and X-ray diffraction structures of [PhCCo3(CO)8]2(dppx) and [Ru66-C)(CO)16]2(dppx)
Authors:William H. Watson   Bhaskar Poola   Jin Liu  Michael G. Richmond
Affiliation:(1) Department of Chemistry, Texas Christian University, Fort Worth, TX 76129, USA;(2) Department of Chemistry, University of North Texas, Denton, TX 76203, USA
Abstract:The reaction of the pincer diphosphine ligand 4,6-bis(diphenylphosphinomethyl)-m-xylene (dppx) with the metal cluster compounds PhCCo3(CO)9 and Ru66-C)(CO)17 has been explored. Both clusters react with dppx to afford the simple substitution products [PhCCo3(CO)8]2(dppx) and [Ru66-C)(CO)16]2(dppx), where two cluster units are tethered by the pincer ligand. The molecular structures of the title products and the 2:1 cluster-pincer ligand stoichiometry have been established by X-ray crystallography. The stability of [PhCCo3(CO)8]2(dppx) and [Ru66-C)(CO)16]2(dppx) has been investigated under gentle thermolysis conditions (ca. 55–65°C). Both dppx-substituted clusters are unstable with [PhCCo3(CO)8]2(dppx) decomposing and [Ru66-C)(CO)16]2(dppx) transforming into the diphosphine-bridged cluster Ru66-C)(CO)15(μ-dppx) as the major observable product. The identity of the latter cluster has been ascertained by IR and NMR spectroscopies and mass spectrometry.
Keywords:Cobalt cluster  ruthenium cluster  diphosphine ligand  pincer ligand  CO substitution
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