ABSTRACT
Reactions of the title complexes and n-BuLi (1.5 equiv, -45 °C) afford functional equivalents of the deprotonated species trans-(C6F5)(p-tol3P)2Pt(C≡C)nLi (n = 2-4), as assayed by subsequent additions of MeI or Me3SiCl to give trans-(C6F5)(p-tol3P)2Pt(C≡C)nMe (66-52%) or trans-(C6F5)(p-tol3P)2Pt(C≡C)nSiMe3 (63-49%). However, 31P NMR data suggest more complicated mechanistic scenarios, and small amounts of the hydride complex trans-(C6F5)(p-tol3P)2PtH (independently synthesized from the chloride complex, AgClO4, and NaBH4) are detected in most cases. Analogous sequences involving trans-(C6F5)(p-tol3P)2Pt(C≡C)2H and benzyl bromide, D2O, or W(CO)6/Me3O+ BF4- similarly afford products with Pt(C≡C)2Bn, Pt(C≡C)2D, or Pt(C≡C)2C(OCH3)=W(CO)5 linkages. The crystal structures of the tungsten and corresponding SiMe3 adduct, the three Pt(C≡C)nMe species, and hydride complex are determined.
