En route to diplatinum polyynediyl complexes trans,trans-(Ar)(R3P)2Pt(C≡C)nPt(PR3)2(Ar): Untold tales, including end-group strategies Conference Paper uri icon

abstract

  • Reactions of {(C6F5)Pt[S(CH2CH 2-)2](μ-Cl)}2 and R3P yield the bis(phosphine) species trans-(C6F5)(R3P) 2PtCl [R = Et (Pt′Cl), Ph, (p-CF3C6H 4)3P; 88-81 %]. Additions of Pt′Cl and H(C≡C)nH (n = 1, 2; HNEt2, 20 mol % CuI) give Pt′C2H (37 %, plus Pt′I, 16 %) and Pt′C 4H (88 %). Homocoupling of Pt′C4H under Hay conditions (O2, CuCl, TMEDA, acetone) gives Pt′C 8Pt′ (85 %), but Pt′C2H affords only traces of Pt′C4Pt′. However, condensation of Pt′C 4H and Pt′Cl (HNEt2, 20 mol % CuI) yields Pt′C4Pt′ (97 %). Hay heterocouplings of Pt′C 4H or trans-(p-tol)(Ph3P)2Pt(C≡C) 2H (Pt*C4H) and excess HC≡CSiEt3 give Pt′C6SiEt3 (76 %) or Pt*C 6SiEt3 (89 %). The latter and wet n-Bu4N + F- react to yield labile Pt*C6H (60 %). Hay homocouplings of Pt*C4H and Pt*C6H give Pt*C8Pt* (64 %) and Pt*C12Pt* (64 %). Reaction of trans-(C6F5)(p-tol3P) 2PtCl (PtCl) and HC≡CH (HNEt2, 20 mol % CuI) yields only traces of PtC2H. However, an analogous reaction with HC≡CSiMe3 gives PtC2SiMe3 (75 %), which upon treatment with silica yields PtC2H (77 %). An analogous coupling of trans-(C6F5)(Ph3P)2PtCl with H(C≡C)2H gives trans-(C6F5)(Ph 3P)2Pt(C≡C)2H (34 %). Advantages and disadvantages of the various trans-(Ar)(R3P)2Pt end-groups are analyzed. © 2008 IUPAC.

author list (cited authors)

  • Stahl, J., Bohling, J. C., Peters, T. B., de Quadras, L., & Gladysz, J. A.

citation count

  • 12

publication date

  • January 2008