Synthesis and characterisation of mono- and dinuclear diethyldithiocarbamatonickel(II) organochalcogenide complexes

The reaction of Ni(dtc)(PR3)Cl (dtc=diethyldithiocarbamate, R=Ph or Bu) with HSC6H4Cl-4 or HSCH2C6H4Cl-4 and Et3N gave two types of complex. For PPh3, the products were [Ni(dtc)(mu-SC6H4Cl-4)](2) (1) and [Ni(dtc)(mu-SCH2C6H4Cl-4)](2) (2); whilst PBu3 gave Ni(dtc)(PBu3)(SC6H4Cl-4) (3). The structure of freshly prepared 3 was determined to be monomeric, as indicated by X-ray diffraction studies. However, at room temperature in solution, 3 was observed to slowly convert to 1. Structural identification of 1 and 2 and similar dimers, and structural identification of 3 and analogous monomers, were investigated by mass spectrometry. Electron impact mass spectrometry (EIMS) failed to confirm the proposed structures due to extensive decomposition in the mass spectrometer. In the electron impact (EI) mode, all complexes invariably decomposed to Ni(dtc),; on the other hand, fast atom bombardment (FAB) ionisation gave the expected molecular ions for all compounds. (C) 1999 Elsevier Science Ireland Ltd. AII rights reserved.