Abstract
Reactions of the title complexes and n-BuLi (1.5 equiv, -45 °C) afford functional equivalents of the deprotonated species trans-(C(6)F(5))(p-tol(3)P)(2)Pt(C≡C)(n)Li (n = 2-4), as assayed by subsequent additions of MeI or Me(3)SiCl to give trans-(C(6)F(5))(p-tol(3)P)(2)Pt(C≡C)(n)Me (66-52%) or trans-(C(6)F(5))(p-tol(3)P)(2)Pt(C≡C)(n)SiMe(3) (63-49%). However, (31)P NMR data suggest more complicated mechanistic scenarios, and small amounts of the hydride complex trans-(C(6)F(5))(p-tol(3)P)(2)PtH (independently synthesized from the chloride complex, AgClO(4), and NaBH(4)) are detected in most cases. Analogous sequences involving trans-(C(6)F(5))(p-tol(3)P)(2)Pt(C≡C)(2)H and benzyl bromide, D(2)O, or W(CO)(6)/Me(3)O(+) BF(4)(-) similarly afford products with Pt(C≡C)(2)Bn, Pt(C≡C)(2)D, or Pt(C≡C)(2)C(OCH(3))=W(CO)(5) linkages. The crystal structures of the tungsten and corresponding SiMe(3) adduct, the three Pt(C≡C)(n)Me species, and hydride complex are determined.