Abstraction of Oxygen from ketones by decachlorodiniobium(V)

Abstract

[Nb2Cl10] abstracts oxygen from 2-butanone and 9-heptadecanone to yield, after hydrolysis, alkanes, chloroalkanes or arylalkanes, depending upon the solvent employed. Extensive rearrangement of alkyl chains was observed and the extent of rearrangement was consistent with the relative stabilities of proposed alkyl oxide-stabilised carbocationic intermediates. The active species appears to be the [Nb2Cl10] molecule. When the [Nb2Cl10]/ketone ratio is less than one, formation of inactive mononuclear species is favoured with consequent lower yields of products. Both coordinated ketone and alkyl oxide intermediates were detected in solution. Preliminary results employing [Mo2Cl10] and [WCl6] are ..