The synthesis of perfluoroalkyl-substituted "pincer"-type PCP ligands, 1,3-C6H4(CH2P(R-f)(2))(2) (R-f = CF3, C2F5), and platinum coordination studies (R-f = CF3) are reported. 1,3-C6H4(CH2P(CF3)(2))(2) ((3PCPH)-P-CF) reacts at ambient temperatures with (cod)Pt(Me)Cl (cod = 1,5-cyclooctadiene) and (cod)PtMe2 to afford unmetalated PCPH-bridged products [((3PCPH)-P-CF)Pt(Me)Cl](x) and cis-[((3PCPH)-P-CF)PtMe2](2), respectively. cis-[((3PCPH)-P-CF)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 ((3PCP)-P-CF)PtCl and((3PCP)-P-CF)PtMe. Treatment of ((3PCP)-P-CF)PtCl with MeMgBr provides an alternative route to ((3PCP)-P-CF)PtMe. The carbonyl cation ((3PCP)-P-CF) Pt(CO)+SbF6-(v(CO) = 2143 cm(-1)) was readily prepared by chloride abstraction with AgSbF6 under 1 atm CO. v(CO) data indicates that RfPCP ligands are electronically analogous to trans acceptor phosphine complexes such as trans-((C2F5)(2)PMe)(2)Pt-(Me)(CO)(+) (v(CO) = 2149 cm(-1)).