Reactions of Platinum Terminal Polyynyl Complexes trans -(C 6 F 5 )( p -tol 3 P) 2 Pt(C≡C) n H ( n = 2-4) and n -BuLi, Generation of Functional Equivalents of Pt(C≡C) n Li Species, and Derivatization with Organic and Inorganic Electrophiles.

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.