Abstract
Cis and trans complexes of the type Pt(ligand)Cl 2 (ligand = Ph 2As(CH 2) nAsPh 2, n = 6–12, 16) have been synthesized, together with the bromo, iodo and thiocyanato derivatives for n = 10 and 12. The cis complexes are essentially dimeric. The complexes have been characterized by elemental analyses, infrared and proton NMR spectroscopy, solid state reflectance and visible/UV spectroscopy and vapor phase osmometry. Formation of the cis or trans isomer for the complexes Pt(ligand)Cl 2 is critically dependent on the choice of complex precursor: potassium tetrachloroplatinate(II) yields the cis isomer, whilst Zeise's salt gives the trans isomer. The bromo, iodo and thiocyanato derivatives prepared via an exchange reaction give cis complexes. Evidence is presented for the existence of PtNCS and PtSCN linkages both in the solid state and in solution for the thiocyanato derivatives. Product distribution and stereochemistry in all of the complexes are discussed in terms of the factors governing trans chelation.
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