Substituted olefin and nitrile complexes of some group VIII metals.

The introduction to the first chapter contains a brief review of olefin and related complexes of formally zerovalent platinum, with particular emphasis on the general applicability of the methods of preparation previously employed by other workers, The preparation of some tetrafluoroethylene and hexafluoropropene complexes of type Pt(olefin)L2 (L= monodentate ligand; L2 = bidentate ligand) are reported by the new route of the ligand displacement of triphenylarsine from pt(olefin) (AsPh3)2. The limitations of this method as a general synthetic route are discussed with illustrations. The infrared and 19F n.m.r. spectra of the pt(C2 F4)L2 and Pt(C3 F6)L2 complexes are presented and discussed, with particular reference to the variation in the values of j (195pt - F) observed for complexes containing different ligands, L. The reactions of some pt(C2 F4)L2 complexes with tetrafluoroethylene, hydrogen chloride and trifluoroacetic acid are also described. Chapter two contains an introductory review of the previously reported examples of pi-bonded nitrile complexes of transition metals, and the crystal structure of pt(CF3 CN) (PPh3)2 . Some reactions of the latter complex are also reported and discussed, Unsuccessful attempts to prepare rhodium and iridium complexes containing pi-bonded trifluoroacetonitrile and chloroacetonitrile are described, along with the isolation of some resulting novel metallocyclic complexes containing nitrile fragments. The introduction to chapter three is a review of the reported modes of coordination of beta-diketones to transition metals. Some complexes of formally zerovalent platinum pt (beta-diketone) (PPh3)2, are described, which are proposed to contain neutral beta-diketones bonded to the platinum, attempts to prepare rhodium(I) complexes containing beta-diketones bonded. in this manner are also reported, but resulted only in the isolation of rhodium(III) beta-diketonato complexes.