Rapid phosphorus–nitrogen bond cleavage in bis(diphenylphosphino)amine. Synthesis, X-ray structure and electrochemical characterization of [Ni2(μ2-Ph2P)(μ2-Ph2PNHPPh)2(CNR)2]X, R=Me, n-Bu, Xylyl; X=Cl, I, BPh4 binuclear Ni(I) complexes

Ni(II) reacts with Ni(0) complexes in toluene solution to yield diamagnetic phosphido-bridging Ni(I)–Ni(I) complexes of the type Ni2(μ2-PPh2)(CNR)2(μ2-dppa)2. The great thermodynamic stability of these complexes is discussed on the light of their electrochemical properties. The X-ray crystal structure of the complexes Ni2(μ2-PPh2)(CNR)2(μ2-dppa)2, R=n-Bu, Xylyl is also presented.