Reactions of Cp*(2)Zn(2) with sterically demanding bis(iminodi(phenyl)phosphorano)methanes LH (LH = CH(2)(Ph(2)P=NR)(2) (R = Ph L(1)H, SiMe(3)L(2)H, 2,6-i-Pr(2)C(6)H(3) (Dipp) L(3)H) at ambient temperature occurred with elimination of Cp*H and subsequent formation of the homoleptic complex L(1)(2)Zn(2)1 and the heteroleptic complexes LZnZnCp* (L = L(2)2, L(3)3, L(1)4). 3 is the first structurally characterized heteroleptic organozinc complex with the zinc atoms in the formal oxidation state +1.