TRANSINFLUENCE ON BOND DISTANCES IN PLATINUM(II) COMPLEXES - STRUCTURES OF TRANS-[PTPHI(ME(2)S)(2)] AND TRANS-[PTI(2)(ME(2)S)(2)]

trans-[Iodophenylbis (dimethylsulfide)platinum(II)] and trans-[diiodob is(dimethylsulfide)platinum(II)] have been synthesized and their cryst al structures determined. Both compounds are monoclinic: trans-[PtPhI( Me(2)S)(2)] crystallizes in P2(1)/c with a=8.7126(4), b=18.779(1), c=9 .1054(4) Angstrom, beta=105.444(7)degrees and Z=4 and trans-[PtI2(Me(2 )S)(2)] in C2/c with a=15.641(2), b=6.046(1), c=12.845(2) Angstrom, be ta=101.67(1) and Z=4. The structures were refined to R=0.054 and R=0.0 39, respectively. The coordination geometry around platinum is slightl y distorted square-planar in both cases. In the trans-diiodo complex, the Pt-I distance is 2.6039(8) Angstrom. When iodide is coordinated tr ans to the phenyl the Pt-I distance is 2.712(1) Angstrom. This increas e of 0.108 Angstrom reflects a large ground state trans influence of p henyl compared to iodide. The complexes maintain their trans configura tions in solution as shown by NMR and Raman spectroscopy.