Selective functionalization of P₄ by metal-mediated C-P bond formation

Sebastian Heinl; Sabine Reisinger; Christoph Schwarzmaier; Michael Bodensteiner; Manfred Scheer

doi:10.1002/anie.201403295

Selective functionalization of P₄ by metal-mediated C-P bond formation

Angew Chem Int Ed Engl. 2014 Jul 14;53(29):7639-42. doi: 10.1002/anie.201403295. Epub 2014 May 30.

Authors

Sebastian Heinl¹, Sabine Reisinger, Christoph Schwarzmaier, Michael Bodensteiner, Manfred Scheer

Affiliation

¹ Institute of Inorganic Chemistry, University of Regensburg, 93040 Regensburg (Germany).

PMID: 24890009
DOI: 10.1002/anie.201403295

Abstract

A new and selective one-step synthesis was developed for the first activation stage of white phosphorus by organic radicals. The reactions of NaCp(R) with P4 in the presence of CuX or FeBr3 leads to the clean formation of organic substituted P4 butterfly compounds Cp(R)2P4 (Cp(R): Cp(BIG)=C5(4-nBuC6H4)5 (1 a), Cp'''=C5H2tBu3 (1 b), Cp*=C5Me5 (1 c) und Cp(4iPr)=C5HiPr4 (1 d)). The reaction proceeds via the activation of P4 by Cp(R) radicals mediated by transition metals. The newly formed organic derivatives of P4 have been comprehensively characterized by NMR spectroscopy and X-ray crystallography.

Keywords: P4 activation; organophosphorus compounds; phosphorus; radicals.