Organocadmium Hydrazide and Hydrazine Complexes

The first structurally authenticated organocadmium hydrazine and hydrazide complexes are reported. Reaction of CdMe2 with H2NN(CH2)4O in a 1:1 ratio forms the adduct [(Me2Cd)3(H2NN(CH2)4O)2]∞ (1) below room temperature. Heating the same solution to 90 oC liberates methane and generates [MeCdN(H)N(CH2)4O]4 (2). The structure of 1 consists of dimers, [Me2Cd·H2NN(CH2)4O]2, which form six-membered Cd2N4 rings, linked into 1-D chains by CdMe2 moieties coordinated to the oxygen of the morpholine ring. 2 is a tetramer embodying a Cd4N8 cage analogous to related organozinc hydrazides, but unlike the latter, each metal center has the same coordination environment. Hydrolysis of 2 gives [MeCdN(H)N(CH2)4O]3[MeCdOH] (3), which is isostructural with its known zinc analogue. In addition to X-ray crystallography, 1 and 2 have been characterized by 1H, 13C, and 113Cd NMR.