Triphosphane formation from the terminal zirconium phosphinidene complex [Cp2ZrPDmp(PMe3)] (Dmp=2,6-Mes2C6H3) and crystal structure of DmpP(PPh2)2

The new terminal phosphinidene complex [Cp2ZrPDmp(PMe3)] (Dmp=2,6-Mes2C6H3; 1) was prepared in 81% yield by the reaction of [Li(Et2O)][P(H)Dmp] with [Cp2Zr(Me)Cl] in the presence of excess PMe3. Compound 1 reacts with Ph2PCl to produce selectively the sterically congested triphosphane DmpP(PPh2)2 (2) and [Cp2ZrCl2] in high yields. The structure of 2 obtained by X-ray diffraction analysis of a single crystal reveals phosphorus–phosphorus bond lengths of 2.251(2) and 2.234(2) Å and a PPP bond angle of 105.46(6)°.