摘要:
Synthetic strategies toward the synthesis of electron-poor pincer complexes ((PCP)-P-CF3)PtH and ((PCP)-P-CF3)Pt(eta(2)-H-2)(+) are described. Metathesis of ((PCP)-P-CF3)PtCl with hydride reagents does not lead to ((PCP)-P-CF3)PtH; ((PCP)-P-CF3)PtCl with KH in tetrahydrofuran (THF) afforded an unusual metallated bimetallic pincer product ((PCP)-P-CF3)Pt[kappa(1)-C,kappa P3-,C,P-2,6-(CHP(CF3)(2))(CH2P(CF3)(2))-C6H3]PtCl, which has been structurally characterized. Chloride abstraction from ((PCP)-P-CF3)PtCl or protonolysis of ((PCP)-P-CF3)PtMe in the presence of H-2 gives the structurally characterized hydride-bridged dimer {((PCP)-P-CF3)Pt}(2)(mu-H)(+). In the presence of trapping ligands H2O, C2H4, or pentafluoropyridine, the corresponding complexes ((PCP)-P-CF3)Pt(L)(+) (L = H2O, C2H4, NC5F5) are cleanly produced and have been structurally characterized. The C2H4 and NC5F5 adducts may be alternatively prepared by methide abstraction from (CF3PCP)PtMe with Ph3C+B(C6F5)(4)(-) in the presence of trapping ligand. Evidence for the transient formation of ((PCP)-P-CF3)PtH from treatment of ((PCP)-P-CF3)PtCl or ((PCP)-P-CF3)Pt(NC5F5)(+) with Et3Si+B(C6F5)(4)(-) is presented. ((PCP)-P-CF3)Pt(C2H4)(+) serves as a catalyst for ethylene hydrogenation (0.30 turnovers h(-1), 70 degrees C) and hydrosilation with Et3SiH (460 turnovers h(-1), RT) and Cl3SiH (5 turnovers h(-1), RT). At elevated temperatures, ((PCP)-P-CF3)Pt(C2H4)(+) also exhibits limited ethylene dimerization activity (0.07 turnovers h(-1), 155 degrees C and 1-butene isomerization (0.9 turnovers h(-1), 80 degrees C).