Synthesis and Platinum Coordination Chemistry of the Perfluoroalkyl Acceptor Pincer Ligand, 1,3-(CH2P(CF3)2)2C6H4

The synthesis of perfluoroalkyl-substituted “pincer”-type PCP ligands, 1,3-C6H4(CH2P(Rf)2)2 (Rf = CF3, C2F5), and platinum coordination studies (Rf = CF3) are reported. 1,3-C6H4(CH2P(CF3)2)2 (CF 3 PCPH) reacts at ambient temperatures with (cod)Pt(Me)Cl (cod = 1,5-cyclooctadiene) and (cod)PtMe2 to afford unmetalated PCPH-bridged products [(CF 3 PCPH)Pt(Me)Cl] x and cis-[(CF 3 PCPH)PtMe2]2, respectively. cis-[(CF 3 PCPH)PtMe2]2 is soluble and has been spectroscopically and crystallographically characterized. Thermolysis of these compounds results in the loss of methane and the formation of metalated complexes (CF 3 PCP)PtCl and (CF 3 PCP)PtMe. Treatment of (CF 3 PCP)PtCl with MeMgBr provides an alternative route to (CF 3 PCP)PtMe. The carbonyl cation (CF 3 PCP)Pt(CO)+SbF6 - (ν(CO) = 2143 cm-1) was readily prepared by chloride abstraction with AgSbF6 under 1 atm CO. ν(CO) data indicates that R f PCP ligands are electronically analogous to trans acceptor phosphine complexes such as trans-((C2F5)2PMe)2Pt(Me)(CO)+ (ν(CO) = 2149 cm-1).