Abstract
The regiospecific 1,2-addition of the hydrogenisocyanide complexes W(CO) 5CNH, Fe(CN) 2(CNH) 4 and [FeCp(dppe)CNH]BF 4 to a total of eight higher alkylated olefins (R 1R 2CCR 3R 4) and cycloolefins (norbornene, cyclohexene) yields a series of mono- (e.g. W(CO) 5CNCR 1R 2CHR 3R 4, [FeCp(dppe)CN-CMe 2CHMe 2]BF 4) and hexaalkyl isocyanide complexes ([Fe(CNCR 1R 2-CHR 3R 4) 6](BF 4) 2) which have been characterized by elemental analysis and NMR ( 1H, 13C), IR (Raman), and mass spectroscopy. The reaction deviates from the general scheme, in that two cyclohexene units couple selectively to both the pentacarbonyltungsten and the cyclopentadienyl(diphosphine)iron systems, to give (1-cyclohexyl)cyclohexyl isocyanide. Frequently, Fe(CN)Cp(dppe)/HBF 4 avoids (cyano) N-alkylation because the unreactive FeCP(CNBF 3)(dppe) is formed instead.
Published Version
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