New Organocadmium Hydrazine Adducts and Hydrazide Complexes

Abstract

The synthesis of (Me2CdL)n [L = H2NN(H)tBu, n = 2 (1); L = H2NN(CH2CH2)2NMe, n = ∞ (2)] and the conversion of 2 to MeCdN(H)N(CH2CH2)2NMe (4) are reported. In the solid state, 1 is a dimer in which each H2NN(H)tBu bridges two metal centres to generate discrete, isolated Cd2N4 rings, whereas 2 is a 1D polymer in which Me2Cd units are bridged by H2N and MeN moieties; the chains in 2 are further reinforced by NH···N hydrogen bonds. Hydrazide 4 is tetrameric and isostructural with the known aminomorpholine analogue; it forms a Cd4N8 cage structure that embodies both five‐membered Cd2N3 and six‐membered Cd2N4 rings. In addition to X‐ray crystallography, 1, 2 and 4 have been characterised by 1H, 13C, and 113Cd NMR spectroscopy.

Zinc, cadmium and mercury

“…44 The air-sensitive cadmium-hydrazine adducts Me 2 Cd(H 2 NX) (X = N(H) t Bu; N(CH 2 ) 4 NMe) have been prepared and characterised in detail, the 1-amino-4-methylpiperazine adduct being shown to undergo photolytic conversion to the tetrameric [MeCdN(H)N(CH 2 ) 4 NMe] 4 , which represents only the second example of an organocadmium hydrazide. 45 It is noteworthy that CdF 2 can now be 'dissolved' in liquid ammonia, by exposing the mixture to air at À40 1C, thus forming [Cd(NH 3 ) 6 ]F 2 .H 2 O. 46 Finally, the gas-phase reaction of group 12 MeM + with NH 3 has been investigated experimentally and theoretically, demonstrating for Zn, Cd and Hg the formation of a C-N bond, with the loss of a neutral-metal as leaving group.…”