The phenyldicyanooxiranes, trans-2,3-dicyano-2,3-diphenyloxirane, 2,2-dicyano-3,3-diphenyloxirane, and 2,2-dicyano-3-phenyloxirane, are cleaved by platinum(O) tertiary phosphine complexes to afford zerovalent metal-olefin complexes and phosphine oxides. The π-olefin products were characterized by 1H and 31P 1H NMR spectroscopy and by an X-ray structure determination of Pt[trans-Ph(CN)CC(CN)Ph](PPh3)2·CH3OH. Deoxygenation of the ring proceeds with retention of configuration in the final two-carbon olefin fragment. The π-complex Pt[Ph2CC(CN)2](PPh3)2 is isolable, but the olefin dissociates in the presence of alternative ligands. While Pd[Ph(H)CC(CN)2](PPh3)2 may be isolated, the analogous complex with Ph2CC(CN)2 cannot be.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry