Abstract
The synthesis of new cationic dithiocarbamate nickel(II) complexes with the mixed-donor bidentate ligands o-Ph 2PC 6H 4CHNR is described. The derivatives of general formula [Ni(R′ 2dtc)( o-Ph 2PC 6H 4CHNR)][ClO 4] [R′= iPr; R=Me ( 1), Et ( 2), iPr ( 3), tBu ( 4); R′= iBu; R=Me ( 5), Et ( 6), iPr ( 7), tBu ( 8)] have been obtained by direct reaction between Ni(ClO 4) 2, the bis(dithiocarbamate) precursors [Ni(R′ 2dtc) 2] and the corresponding iminophosphine. Analogous reaction using [Ni(R′xan) 2] as starting materials allowed the preparation of complexes [Ni(R′xan)( o-Ph 2PC 6H 4CHNR)][ClO 4] [R′=Et; R=Me ( 9), Et ( 10), iPr ( 11), tBu ( 12); R′= iPr; R=Me ( 13), Et ( 14), iPr ( 15), tBu ( 16)]. The new complexes have been characterized by partial elemental analyses, conductivity measurements and spectroscopic methods (IR, 1H and 31P{ 1H} NMR). The X-ray structures of complexes ( 1), ( 5) and ( 13) are reported, revealing that the iminophosphine acts as chelating ligand with coordination around the nickel atom distorted from the square-planar geometry.
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