Abstract
The osmium isocyanide complexes Os 3(CO) 11(CNR) ( 1a, R Pr; 1b, R iPr; 1c, R CH 2Ph; 1d R Ph) are synthesized in high yields by reaction of Os 3(CO) 12 with phosphine imides via a deoxygenation mechanism. These complexes react with an additional equivalent of Ph 3PNR to yield the diisocyanide complexes Os 3(CO) 10(CNR) 2 ( 2a, R Pr; 2b, R iPr; 2c, R CH 2 Ph; 2d, R Ph). The reaction of Os 3(CO) 10(CNCH 2Ph) 2 with excess Ph 3PNPr or Ph 3PNCH 2Ph in refluxing benzene gives Os 3(CO) 9(CNCH 2Ph) 2(CNR) ( 3a, R Pr; 3b, R CH 2Ph). The ruthenium isocyanide derivatives Ru 3(CO) 11(CNR) ( 4a, R Pr; 4b, R iPr, 4c, R CH 2Ph; 4d, R Ph) are also prepared by reaction of Ru 3(CO) 12 with phosphine imide. It was observed that geometrical and electronic characteristics of the imide play key roles in controlling the rate of the reaction.
Published Version
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