Selective dehydrocoupling of phosphines by triamidoamine zirconium catalysts

New zirconium triamidoamine complexes (N3N)ZrR (N3N = N(CH2CH2NSiMe3)(3)(3-); R = Me, < BO > 1 ; PHPh, < BO > 2 ; PHCy, < BO > 4) are effective catalysts for the dehydrocoupling of primary and secondary phosphines and select for the diphosphine product. Mechanistic analysis revealed that metal-catalyzed P-P bond formation occurs via sigma-bond metathesis steps.