Dimethylthiophosphoryl hydrazone ligands and their copper complexes: crystal structures and analysis of their solution complexation behaviour by electrospray mass spectrometry

Four new thiophosphoryl ligands containing NNPS or CNPS connectivities have been prepared and three of them characterised by single-crystal X-ray diffraction. The complexation of these ligands with salts of CuI, CuII, NiII and ZnII has been studied by electrospray mass spectrometry and uv-visible spectrophotometry in acetonitrile and methanol solution. Evidence for 1∶1 and 2∶1 complexation is presented. Two copper(I) complexes were isolated including a mixed chloride–bromide copper(I) complex in which a dimeric structure is adopted with a 22-membered metallacycle.