SYNTHESIS, CHARACTERIZATION AND X-RAY STRUCTURE OF A 5-COORDINATE PLATINUM(II) CATIONIC COMPLEX, BIPYRIDINECHLORO(OMICRON-ISOPROPENYL-N,N-DIMETHYLANILINE)-PLATINUM(II)PERCHLORATE

Reaction of dichloro(o-isopropenyl-N,itN-dimethylaniline)platinum(II), PtCl2(IMN), with 2,2′-bipyridine and sodium perchlorate gives the title compound [Pt(bipy)Cl(IMN)]ClO4 (I). NMR, IR, and X-ray studies show that the cation in I is formally five coordinate both in solution and in the solid state. The X-ray structure of I has been determined using 693 diffractometer data with I/σ(I) ≥ 2.0, and full matrix refinement has given an R of 0.068. Crystals of I are monoclinic, spacegroup P21/c, a 16.715(9), b 10.278(6), c 13.990(8) Å, β 107.24°, Z = 4. The ligand arrangement about the platinum(II) atom of the cation is very distorted trigonal bipyramidal with the olefin and the bipyridine groups in the equatorial plane. The angle substended at the platinum atom by the bipyridine donor atoms is only 77°. A 3c-4e bond, formed by overlap of an empty PtII dsp2 orbital with the filled bipyridine nitrogen sp2 orbitals, is proposed, which allows the complex to the classified as obeying the 16e rule. © 1979.