Abstract
Abstract The reaction of a five-membered (η1-P,η1-C-phosphinocarbene)tetracarbonyl-chromium chelate with several electron-rich triple bonds including an ynamine, a cyanamide and an ethoxyacetylene gives stable seven-membered phosphametallacycles via the insertion of the triple bond into the chromium—carbene bond. With an excess of ethoxyacetylene, a double insertion also takes place leading to a nine-membered phosphametallacycle whose structure has been established by X-ray analysis. A CC double bond of this cycle is loosely coordinated to the Cr(CO)3 group: CCr = 2.384(4) and 2.619(4) A. This first example of a stable double insertion product of a CC triple bond into a metal—carbene bond probably owes its stability to its phosphinocarbene chelate structure.
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