Structural diversity of cadmium(II) complexes of tetraorganodichalcogenoimidodiphosphinato ligands: Monomeric Cd[(SPMe2)2N]2, dinuclear [Cd{(OPMe2)(SPPh2)N}2]2 and [Cd2{(OPPh2)2N}4(H2O)], and trinuclear K[Cd2{(OPPh2)2N}5]

Cadmium complexes of the type View the MathML sourceCd[(XPR2)(YPR2′)N]2(X,Y=O,S;R,R′=Me,Ph) were obtained by reacting CdCl2 and View the MathML sourceK[(XPR2)(YPR2′)N] in a 1:2 molar ratio. The compounds were characterized by IR, multinuclear NMR (1H, 13C, 31P) spectroscopy and mass spectrometry. The molecular structures of Cd[(SPMe2)2N]2 (1), Cd[(OPMe2)(SPPh2)N]2 (4), [Cd2{(OPPh2)2N}4(H2O)] (7 · H2O) and K[Cd2{(OPPh2)2N}5] (8) were established by single-crystal X-ray diffraction. Colourless crystals of 8 were isolated, along with those of 7 · H2O, during recrystallization of crude Cd[(OPPh2)2N]2 (7). A monomeric structure with a tetrahedral CdS4 core is found for 1, whereas 4 contains discrete dimers formed through two O,O′, S-bimetallictriconnective ligand units resulting in distorted trigonal bipyramidal CdO3S2 cores. In the dinuclear compound 7 · H2O the Cd atoms are also bridged by two O,O′,O′-bimetallic triconnective ligands, but the coordination of the metal centres is completed by a bridging water molecule to givedistorted octahedral CdO6 cores. In the trimetallic unit of 8 the K atom is accommodated in the cavity described by the oxygen atoms of three ligand units which bridge the Cd atoms. The remaining two ligands are each one chelating a Cd atom, thus resulting in distorted square pyramidal CdO5 cores.