Abstract

Four new triphenylgermylruthenium carbonyl compounds HRu(CO)4GePh3, 14; Ru(CO)4(GePh3)2, 15; Ru2(CO)8(GePh3)2, 16; and Ru3(CO)9(GePh3)3(μ-H)3, 17 were obtained from the reaction of Ru(CO)5 with Ph3GeH in hexane solvent at reflux, 68 °C. The major product 14 was formed by loss of CO from the Ru(CO)5 and an oxidative addition of the GeH bond of the Ph3GeH to the metal atom. This six coordinate complex contains one terminal hydrido ligand. Compound 15 is formed from 14 and contains two trans-positioned GePh3 ligands in the six coordinate complex. Compound 16 contains two Ru(CO)4(GePh3) fragments joined by an Ru–Ru single bond. Compound 17 contains a triangular cluster of three ruthenium atoms with three bridging hydrido ligands and one terminal GePh3 ligand on each metal atom. When heated to 125 °C, 14 was converted to the new triruthenium compound Ru3(CO)10(μ-GePh2)2, 18. Compound 18 consists of a triangular tri-ruthenium cluster with two GePh2 ligands bridging two different edges of the cluster and one bridging CO ligand. Ru3(CO)12 was found to react with Ph3GeH at 97 °C to yield three products: 15, and two new compounds Ru3(CO)9(μ-GePh2)3, 19 and Ru2(CO)6(μ-GePh2)2(GePh3)2, 20 were obtained. Compound 19 is similar to 18 having a triangular tri-ruthenium cluster but has three bridging GePh2 ligands, one on each Ru–Ru bond. Compound 20 contains only two ruthenium atoms joined by a single Ru–Ru bond that has two bridging GePh2 ligands and a terminal GePh3 ligand on each metal atom. All compounds were characterized by a combination of IR, 1H NMR, single-crystal X-ray diffraction analyses.

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