Studies on Zn(II) and Cd(II) heteroligand complexes with RC(S)NHP(O)(OiPr)2 (R = Ph, NH2, PhNH) and α-diimine (bpy and phen) ligands. C–Cl bond cleavage of CH2Cl2 by [Zn(phen){PhC(S)NP(O)(OiPr)2}2]

The reaction of [ZnLI,II2] (LI = [NH2C(S)NP(O)(OiPr)2]−; LII = [PhNHC(S)NP(O)(OiPr)2]−) or [Cd2LIV4] (LIV = [PhC(S)NP(O)(OiPr)2]−) with 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) leads to the heteroligand complexes [Zn(bpy)LI,II2], [Zn(phen)LI,II2], [Cd(bpy)LIV2] or [Cd(phen)LIV2], respectively. The introduction of the diimine ligands into the coordination sphere of the metal cation provokes a change from 1,5-O,S- to 1,3-N,S-coordination of the anionic ligands for Zn but not for the Cd species. The reaction of [Zn(phen)LIV2] (LIV = PhC(S)NP(O)(OiPr)2−) with CH2Cl2 cleaves the chlorine atoms from CH2Cl2 and leads to the formation of [Zn(phen)LIVCl] and S,S′-bis(benzimidothio-N-diisopropoxyphosphoryl)methane (LIV–CH2–LIV) in high yields. Using CHCl3 or CCl4 instead of CH2Cl2 does not lead to the formation of chlorine substituted products even under reflux conditions. The new compounds were investigated by 1H and 31P{1H} NMR, IR spectroscopy and microanalysis. Crystal structures of [ZnLII2], [Cd(phen)LIV2]·CH2Cl2, [Zn(bpy)LI2] and [Zn(phen)LIVCl] were elucidated by X-ray diffraction.