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Dehydrohalogenation by a Germylene:  Conversion of Carbene Ligands into Carbynes at Ruthenium

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posted on 05.12.2005, 00:00 by Stephen R. Caskey, Michael H. Stewart, Yi Joon Ahn, Marc J. A. Johnson, Jeff W. Kampf
The dialkylgermylene [Ge(CH[SiMe3]2)2] (3) converts the carbene complexes [Ru(CHR)(PCy3)2Cl2] (R = p-C6H4Me [2], n-C4H9 [6]) into the corresponding square-planar carbyne complexes [Ru(CR)(PCy3)2Cl] (R = p-C6H4Me [1], n-C4H9 [7]) cleanly within minutes at 25 °C in benzene; addition of HCl to a benzene solution of 1 results in quantitative re-formation of 2. Replacement of chloride in 1 affords other halide and pseudohalide complexes, [Ru(C-p-C6H4Me)(PCy3)2X] (X = p-OC6H4-t-Bu, Br, F, O3SCF3), cleanly.