Reactions of Platinum Terminal Polyynyl Complexes -(CF)(-tolP)Pt(C≡C)H ( = 2-4) and -BuLi, Generation of Functional Equivalents of Pt(C≡C)Li Species, and Derivatization with Organic and Inorganic Electrophiles.

Reactions of the title complexes and -BuLi (1.5 equiv, -45 °C) afford functional equivalents of the deprotonated species -(CF)(-tolP)Pt(C≡C)Li ( = 2-4), as assayed by subsequent additions of MeI or MeSiCl to give -(CF)(-tolP)Pt(C≡C)Me (66-52%) or -(CF)(-tolP)Pt(C≡C)SiMe (63-49%). However, P NMR data suggest more complicated mechanistic scenarios, and small amounts of the hydride complex -(CF)(-tolP)PtH (independently synthesized from the chloride complex, AgClO, and NaBH) are detected in most cases. Analogous sequences involving -(CF)(-tolP)Pt(C≡C)H and benzyl bromide, DO, or W(CO)/MeO BF similarly afford products with Pt(C≡C)Bn, Pt(C≡C)D, or Pt(C≡C)C(OCH)=W(CO) linkages. The crystal structures of the tungsten and corresponding SiMe adduct, the three Pt(C≡C)Me species, and hydride complex are determined.