Straightforward construction of a rare-earth diphosphanato complex from white phosphorus: synthesis and reactivity

Abstract

The direct construction of functionalized diphosphine ligands from P₄ is a highly valuable but challenging transformation. In this work, a simple method has been developed for the direct formation of an amido-functionalized diphosphanato ligand from a silyl-bridged amido/methylene yttrium complex and white phosphorus. The resulting amido-functionalized diphosphanato yttrium complex 2 has proved to be a useful intermediate for further diversification of the diphosphine ligand through the metal template procedure, for which no evident limitations are enforced by initially present substituents and ancillary ligands, and some unprecedented reactivity patterns of the RPPR unit are revealed. The results described here demonstrate that appending a strongly coordinative substituent to the alkyl ligand together with a coordination to rare earth ions is an efficient strategy for controlling the cleavage modes of P₄ during alkylation and the reactivity of the resulting diphosphanato complex.