Reactivity of electrophilic (mu)-phosphinidene complexes with heterocumulenes: formation of the first (sigma)-(pi)aminophosphaimine complexes [Mn2(CO)8{(mu)-(eta)^1,(eta)^2-P(NiPr2)NR}] and diazoalkane insertions into metal–phosphorus bonds

The bridging phosphinidene complexes [Mn2(CO)8((mu)-PNiPr2)] and [Co2(CO)4((mu)-dppm)((mu)-PNR2)](NR2= NiPr2, TMP) react with heterocumulenes RN3, CH2N2 and Ph2CNN to form complexes with (mu)-(eta)^1,(eta)^2-aminophosphaimine, (mu)-(eta)^1,(eta)^2aminophosphaalkene and (mu)-(eta)^1,(eta)^2-aminophosphadiphenylmethylazaimine ligands, respectively.