Organophosphorus chemistry. Part XII. Reactions of tetramethylbiphosphine and tetrakis(trifluoromethyl)biphosphine with olefins

Abstract

Tetramethylbiphosphine reacts readily with olefins (C₂H₄, CH₂:CF₂, CH₂:CHF, C₃H₆) under the action of u.v. light, to give the corresponding 1,2-bis(dimethylphosphino)ethanes, but does not react at 100° in the dark. Tetrakis-(trifluoromethyl)biphosphine also gives the corresponding diphosphinoethanes in excellent yield when irradiated with olefins (C₂H₄, C₂F₄, C₃H₆, cis- and trans-MeCH:CHMe, CH₂:CHF, CH₂:CF₂) and also, although much more slowly, at 50° in the absence of light. Tetramethylbiphosphine disulphide gives only breakdown products when heated with fluoro-olefins (CH₂:CF₂, CH₂:CHF).