PCP Ligand Research Articles

Complexes of High-Valent Rhenium Supported by the PCP Pincer

The PCP ligand can be introduced into the coordination sphere of Re by metalation in a reaction with L2Re(O)Cl3 precursors, leading to an octahedral (PCP)Re(O)Cl2 (2), in which the aryl donor of PCP is cis to the oxo ligand. Halide exchange with Me3SiBr or Me3SiI furnished analogous (PCP)Re(O)Br2 (3) and (PCP)Re(O)I2 (4). Treatment of 2 with LiAlH4 resulted in the isolation of (PCP)ReH6 (5) upon workup. NMR data suggest a classical hexahydride nature for 5. 5 reacted with PMe3 and 4-dimethylaminopyridine (DMAP) by losing H2 and forming adducts (PCPiPr)ReH4(PMe3) (6) and (PCP)ReH4(DMAP) (7). On the other hand, reaction of 5 with CO resulted in loss of all the hydrides and formation of the Re(I) compound (PCPiPr)Re(CO)3 (8). Finally, thermolysis of the hexahydride 5 led to loss of half the hydrides as H2 and formation of the dimeric species formulated as (PCPiPr)2Re2H6 (9).

One-Pot Synthesis of 1,3-Bis(phosphinomethyl)arene PCP/PNP Pincer Ligands and Their Nickel Complexes

A one-pot synthesis of arene-based PCP/PNP ligands has been developed. The reaction of 1,3-bis(bromomethyl)benzene or 2,6-bis(bromomethyl)pyridine with various chlorophosphines in acetonitrile afforded bis-phosphonium salts. These salts can then be reduced by magnesium powder to yield PCP or PNP ligands. In comparison to traditional synthetic methods for making PCP/PNP ligands involving the use of secondary phosphines, this new alternative method allows for the use of chlorophosphines, which are cheaper, safer to handle, and have a broader range of commercially available derivatives. This is especially true for the chlorophosphines with less bulky alkyl groups. Moreover, the one-pot procedure can be extended to allow for the direct synthesis of PCP/PNP nickel complexes. By using nickel powder as the reductant, the resulting nickel halide was found to directly undergo metalation with the PCP or PNP ligand to generate nickel complexes in high yields.

Different Coordination Modes of the Ph2PCsp3PPh2 Pincer Ligand in Rhodium Complexes as a Consequence of Csp3–H Metal Interaction

Starting from commercially available 4,4′-di-tert-butyldiphenylmethane the pincer ligand bis(4-tert-butyl-2-(diphenylphosphino)phenyl)methane (PCP) was prepared in two steps in moderate yield. Treatment of a solution of RhCl3·3H2O in a mixture of isopropyl alcohol and toluene with equimolar amounts of PCP gave the dimeric rhodium complex 1. In an electrophilic metalation a facially coordinated pincer complex is formed. When PCP is treated with [CODRhCl]2 in a solution of pyridine, the square-pyramidal complex 2 is generated where the bis-phosphine PCP acts as bidentate ligand that coordinates in a cis fashion. SnCl2 inserts into the Rh–Cl bond of 2, which results in an oxidative addition of one of the methylene C–H bonds to form the Rh(III) complex 3, where the PCP ligand coordinates in a meridional way. A 2 equiv portion of PCP reacts with 1 equiv of [CODRhCl]2 in the presence of the electron-donating ligands HPhPC6H4NMe2, PPh2Py, and PPh3, respectively, as well as with stanna- and germa-closo-dodecabora...

Versatile Syntheses of Optically Pure PCE Pincer Ligands: Facile Modifications of the Pendant Arms and Ligand Backbones

A series of chiral C-stereogenic PCP and PCN ligand precursors were prepared in situ from inexpensive achiral starting materials via a simple catalytic asymmetric P–H addition reaction in good overall yields. This facile catalytic method of preparing the ligand backbones renders easy and economical modifications of the electronically crucial para-substituent, chiral functionalities, and donor atoms for different transition metal ions. A one-pot synthetic procedure was used efficiently to prepare the corresponding optically pure pincer complexes. All the new complexes were characterized by NMR and mass spectroscopy. The molecular structures of several selected complexes have also been elucidated by X-ray crystallography. Preliminary studies indicated that minor structural changes on these novel pincer complexes affect their chemical properties significantly when they were applied as catalysts for the reaction between diphenylphosphine and chalcone.

Selective hydration of nitriles to amides catalysed by PCP pincer supported nickel(II) complexes.

The (PCP)Ni-OH complexes (R = (i)Pr, (t)Bu, Cy) are effective catalyst precursors for the selective hydration of nitriles to the corresponding amides under relatively mild conditions (80 °C) and low catalyst loadings (0.05-0.5%). Substrate scope includes aliphatic, vinylic and aromatic nitriles, but substrates with protic groups poison the catalyst abruptly. The catalysts are effective because the electron rich nature of the PCP ligands and their steric bulk renders the hydroxo group labile.

Supramolecular structure of Cu(II) and Zn(II) complexes based on 2,2′:6′,2″-terpyridine, thermal and biological studies

Two supramolecular metal complexes [Cu(II)(terpy)(PCP)(NO3)](1) and [Zn(II)(terpy)(NO3)2](2) (terpy=2,2′:6′,2″-terpyridine) (PCP = Pentacyanopropenide) were synthesized and structurally characterized by Single-crystal X-ray diffraction. Single-crystal X-ray diffraction revealed that the PCP ligand coordinated to Cu(II) ion through one CN group, and it was absent from the coordination sphere of Zn(II) complex. In complexes (1) and (2), 1D chain was formed through C1–H1···O1 and C4–H4···O2 hydrogen-bonding interactions, respectively. The crystal structure was further stabilized by π–π stacking interactions. The thermal stabilities of these compounds were investigated. Furthermore, antimicrobial activities of these compounds were investigated against eight types of bacteria. The copper complex exhibited a significant activity against three types of bacteria with minimal inhibitory concentrations (MICs) under one microgram per milliliter.

Conformational Flexibility of Dibenzobarrelene-Based PC(sp3)P Pincer Iridium Hydride Complexes: The Role of Hemilabile Functional Groups and External Coordinating Solvents

Bifunctional dibenzobarrelene-based PC(sp3)P pincer iridium complex 1 is known as an efficient catalyst in acceptorless dehydrogenation of alcohols and hydrogenation/hydroformylation of alkenes. In order to shed light on the mechanism of the hydrogen formation/activation, we performed variable-temperature IR and NMR (1H, 31P) analysis of intra- and intermolecular interactions involving a hydride ligand and hydroxymethyl cooperating group in 1 and its analogues. The results of the spectroscopic measurements in different media (dichloromethane, toluene, DMSO, and mixed solvents) were compared with the quantum chemical (DFT/M06 and B3PW91) calculations. The obtained data imply flexibility of the dibenzobarrelene-based scaffold, unprecedented for conventional pincer ligands. Both the CH2OH-substituted complex 1 and its COOEt analogue 3 prefer facial configuration of the PCP ligand with a P–Ir–P angle of ca. 100°. Such geometries are stabilized by Ir···O interaction with the dangling functional group and differ by the mutual arrangement of the H and Cl ligands. The complexes show dynamic equilibrium between the two most stable fac-isomers, which can be transformed into the meridional ones in the presence of coordinating additives (CH3CN, DMSO, or CO, but not Et3N). The process is reversible for CH3CN but irreversible for DMSO and CO, in agreement with the Lewis basicity of these molecules.

Addition of C-C and C-H bonds by pincer-iridium complexes: a combined experimental and computational study.

We report that pincer-ligated iridium complexes undergo oxidative addition of the strained C-C bond of biphenylene. The sterically crowded species ((tBu)PCP)Ir ((R)PCP = κ(3)-1,3-C6H3(CH2PR2)2) initially reacts with biphenylene to selectively add the C(1)-H bond, to give a relatively stable aryl hydride complex. Upon heating at 125 °C for 24 h, full conversion to the C-C addition product, ((tBu)PCP)Ir(2,2'-biphenyl), is observed. The much less crowded ((iPr)PCP)Ir undergoes relatively rapid C-C addition at room temperature. The large difference in the apparent barriers to C-C addition is notable in view of the fact that the addition products are not particularly crowded, since the planar biphenyl unit adopts an orientation perpendicular to the plane of the (R)PCP ligands. Based on DFT calculations the large difference in the barriers to C-C addition can be explained in terms of a "tilted" transition state. In the transition state the biphenylene cyclobutadiene core is calculated to be strongly tilted (ca. 50°-60°) relative to its orientation in the product in the plane perpendicular to that of the PCP ligand; this tilt results in very short, unfavorable, non-bonding contacts with the t-butyl groups in the case of the (tBu)PCP ligand. The conclusions of the biphenylene studies are applied to interpret computational results for cleavage of the unstrained C-C bond of biphenyl by ((R)PCP)Ir.

Synthesis and Catalytic Property of Iron Pincer Complexes Generated by Csp3–H Activation

When the diphosphinito PCP ligand (Ph2P(C6H4))2CH2 (1) was treated with Fe(PMe3)4 and FeMe2(PMe3)4, the Csp3–H activation products [(Ph2P(C6H4))2CH]Fe(H)(PMe3)2 (2) and [(Ph2P(C6H4))(PhP(C6H4)2)CH]Fe(PMe3)2 (3) were obtained at room temperature. The generation of product 3 underwent one Csp3–H and one Csp2–H bond activation process. The new iron hydride complex 2 showed good activity in the catalytic hydrosilylation of aldehydes and ketones by using (EtO)3SiH as the hydrogen source under mild conditions. Complexes 2 and 3 were characterized by spectroscopic methods and X-ray diffraction analysis.

Kinetics and Thermodynamics of Small Molecule Binding to Pincer-PCP Rhodium(I) Complexes

The kinetics and thermodynamics of the binding of several small molecules, L (L = N2, H2, D2, and C2H4), to the coordinatively unsaturated pincer-PCP rhodium(I) complexes Rh[(t)Bu2PCH2(C6H3)CH2P(t)Bu2] (1) and Rh[(t)Bu2P(CH2)2(CH)(CH2)2P(t)Bu2] (2) in organic solvents (n-heptane, toluene, THF, and cyclohexane-d12) have been investigated by a combination of kinetic flash photolysis methods, NMR equilibrium studies, and density functional theory (DFT) calculations. Using various gas mixtures and monitoring by NMR until equilibrium was established, the relative free energies of binding of N2, H2, and C2H4 in cyclohexane-d12 were found to increase in the order C2H4 < N2 < H2. Time-resolved infrared (TRIR) and UV-vis transient absorption spectroscopy revealed that 355 nm excitation of 1-L and 2-L results in the photoejection of ligand L. The subsequent mechanism of binding of L to 1 and 2 to regenerate 1-L and 2-L is determined by the structure of the PCP ligand framework and the nature of the solvent. In both cases, the primary transient is a long-lived, unsolvated species (τ = 50-800 ns, depending on L and its concentration in solution). For 2, this so-called less-reactive form (LRF) is in equilibrium with a more-reactive form (MRF), which reacts with L at diffusion-controlled rates to regenerate 2-L. These two intermediates are proposed to be different conformers of the three-coordinate (PCP)Rh fragment. For 1, a similar mechanism is proposed to occur, but the LRF to MRF step is irreversible. In addition, a parallel reaction pathway was observed that involves the direct reaction of the LRF of 1 with L, with second-order rate constants that vary by almost 3 orders of magnitude, depending on the nature of L (in n-heptane, k = 6.7 × 10(5) M(-1) s(-1) for L = C2H4; 4.0 × 10(6) M(-1) s(-1) for L = N2; 5.5 × 10(8) M(-1) s(-1) for L = H2). Experiments in the more coordinating solvent, THF, revealed the binding of THF to 1 to generate 1-THF, and its subsequent reaction with L, as a competing pathway.

Acetonitrile Coupling at an Electron‐Rich Iridium Center Supported by a PCP Pincer Ligand

AbstractAryl amido iridium complexes supported by a tridentate phosphanyl–carbene–phosphanyl pincer ligand [(PCP)Ir–N(H)Ar, Ar = C6H5, 1a; Ar = 2,6‐iPr2C6H3, 1b] react with acetonitrile to afford the dimeric complex 2, in which two (PCP)Ir fragments are bridged by a diiminato ligand derived from two molecules of CH3CN. Metrical parameters obtained from X‐ray structural determination of 2 confirm that the bridging ligand is a diiminato species rather than an enediamido moiety, which indicates that the reductive coupling is mediated by one electron per iridium center. Experiments suggest that the reaction proceeds by heterolytic cleavage of the Ir–N(H)Ar bond followed by one‐electron reduction of the resulting IrI–NCCH3 cation by the amido anion. The resulting anilino radical rapidly abstracts a hydrogen atom from the solvent. The reductive coupling of acetonitrile at a late transition metal center is unusual and in this instance occurs as a result of the highly σ‐donating, electron‐rich nature of the PCP ligand.

Experimental and Computational Studies of the Reaction of Carbon Dioxide with Pincer-Supported Nickel and Palladium Hydrides

A series of Ni(II) and Pd(II) hydrides supported by PNP and PCP ligands, including iPr2PNP(CH3)PdH (iPr2PNP(CH3) = N(2-PiPr2-4-MeC6H3)2), iPr2PNP(CH3)NiH, iPr2PNP(F)PdH (iPr2PNP(F) = N(2-PiPr2-4-C6H3F)2), CyPhPNPPdH (CyPhPNP = N(2-P(Cy)(Ph)-4-MeC6H3)2), tBu2PCPPdH (tBu2PCP = 2,6-C6H3(CH2PtBu2)2), tBu2PCPNiH, Cy2PCPPdH (Cy2PCP = 2,6-C6H3(CH2PCy2)2), and Cy2PCPNiH, were prepared using literature methods. In addition, the new Ni and Pd hydrides Cy2PSiPMH (M = Ni, Pd; Cy2PSiP = Si(Me)(2-PCy2-C6H4)2) supported by PSiP ligands were synthesized. The analogous metal hydride complexes supported by the Ph2PSiP ligand (Ph2PSiP = Si(Me)(2-PPh2-C6H4)2) could not be prepared. Instead, the Ni(0) and Pd(0) η2-silane complexes Ph2PSiHPM(PPh3) (M = Ni, Pd; Ph2PSiHP = (H)Si(Me)(2-PPh2-C6H4)2), which have been proposed to be in equilibrium with Ph2PSiPMH (M = Ni, Pd) and PPh3, were prepared. Facile carbon dioxide insertion into the metal–hydride bond to form the metal formate complexes tBu2PCPM-OC(O)H (M = Ni, Pd) or Cy2PCPM-OC(O)H (M = Ni, Pd) was observed for PCP-supported species, and a similar reaction was observed for Cy2PSiP-supported hydrides to form Cy2PSiPM-OC(O)H (M = Ni, Pd). No reaction with carbon dioxide was observed for any complexes supported by PNP ligands. The η2-silane complex Ph2PSiHPPd(PPh3) reacted rapidly with carbon dioxide to give Ph2PSiPPd-OC(O)H and PPh3, while the corresponding Ni complex Ph2PSiHPNi(PPh3) did not react with carbon dioxide. DFT calculations indicate that carbon dioxide insertion is thermodynamically favorable for PSiP- and PCP-supported hydrides because the strong trans influence of the anionic carbon donor destabilizes the metal–hydride bond. In contrast, carbon dioxide insertion is thermodynamically unfavorable for the PNP-supported species. In the case of the η2-silane complexes, carbon dioxide insertion is thermodynamically favorable for Pd and unfavorable for Ni. This is because the equilibrium between the metal hydride and PPh3 and the η2-silane complex more strongly favors the metal hydride for Pd than for Ni. In the cases of metal hydrides, the thermodynamic favorability of carbon dioxide insertion can be predicted from the natural bond orbital charge on the hydride. The pathway for carbon dioxide insertion into the metal hydride is concerted and features a four-centered transition state. The energy of the transition state for carbon dioxide insertion decreases as the trans influence of the anionic donor of the pincer ligand increases.

Room Temperature, Palladium-Mediated P–Arylation of Secondary Phosphine Oxides

We show that a broad range of aryl iodides are efficiently coupled with secondary phosphine oxides using 1 mol % of a catalyst formed in situ from tris(dibenzylideneacetone)dipalladium and Xantphos (1). Scalemic (S)-methylphenylphosphine oxide [(S)-2e] is shown to undergo arylation without detectable stereoerosion. The application of this method to the synthesis of novel P-chiral phosphines and PCP ligands is demonstrated.

Bis(3-carboxy-5-nitrobenzoato)bis[2-(pyridin-4-yl)-1H-imidazo[4,5-f][1,10]phenanthroline]manganese(II)

In the title compound, [Mn(C8H4NO6)2(C18H11N5)2], the MnII atom is six-coordinated by two N,N′-bidentate 6-(pyridin-4-yl)-5H-cyclo­penta­[f][1,10]phenanthroline (pcp) ligands and two carboxyl­ate O atoms from two monodentate 3-carb­oxy-5-nitro­benzoate anions in a distorted cis-MnO2N4 octa­hedral arrangement. Within the pcp ligands, the dihedral angles between the polycyclic skeletons and pendant pyridine rings are 6.2 (2) and 8.3 (2)°. In the crystal, mol­ecules are linked by O—H⋯N and N—H⋯O hydrogen bonds. Several aromatic π–π stacking inter­actions [shortest centroid–centroid separation = 3.516 (3) Å] are also observed.

Activation of sp3 Carbon−Hydrogen Bonds by Cobalt and Iron Complexes and Subsequent C−C Bond Formation

The sp3 C−H bond activation induced by CoMe(PMe3)4 and FeMe2(PMe3)4 was investigated. C(sp3)-cyclometalated complexes, based on diphosphinito PCP ligand (Ph2POCH2)2CH2, Co{(Ph2POCH2)2CH}(PMe3)2 (1), and Fe{(Ph2POCH2)2MeC}(H)(PMe3)2 (2), were obtained under mild conditions. Iodomethane is oxidatively added to 1, affording Co{(Ph2POCH2)2CH}(PMe3)(Me)(I) (3). Monocarbonylation of the hydrido-iron complex 2 occurs with substitution of a trimethylphosphine ligand trans to the hydrido ligand, affording Fe{(Ph2POCH2)2MeC}(H)(CO)(PMe3) (4). The reaction of 2 with phenylacetylene delivered the demetalated new diphosphine ligand (Ph2POCH2)2CHCH3 (6) and bis(phenylethinyl)iron complex Fe(PhCC)2(PMe3)4 (5). The new complexes 1−4 were characterized by spectroscopic methods and by X-ray diffraction analysis.

Synthesis, Characterization, and Reactivity of Nickel Hydride Complexes Containing 2,6-C6H3(CH2PR2)2(R =tBu,cHex, andiPr) Pincer Ligands

The syntheses and full characterization of nickel hydrides containing the PCP "pincer"-type ligand, where PCP = 2,6-C(6)H(3)(CH(2)PR(2))(2) (R = tBu, cHex, and iPr), are reported. These Ni-H complexes are prepared by the conversion of ((R)PCP)NiCl precursors into the corresponding nickel hydrides by use of appropriate hydride donors. Surprisingly, although the ((R)PCP)NiCl precursors are quite similar chemically, the conversions to the hydrides were not straightforward and required different hydride reagents to provide analytically pure products. While NaBH(4) was effective in the preparation of pure ((tBu)PCP)NiH, Super-Hydride solution (LiEt(3)BH in THF) was required to prepare either ((cHex)PCP)NiH or ((iPr)PCP)NiH. Attempts to prepare a Ni-H from ((Ph)PCP)NiCl with a variety of hydride reagents yielded only the free ligand as an identifiable product. Two of the derivatives, tBu and cHex, have also been subjected to single crystal X-ray analysis. The solid-state structures each showed a classic, near-square planar arrangement for Ni in which the PCP ligand occupied three meridional ligand points with the Ni-H trans to the Ni-C bond. The resulting Ni-H bond lengths were 1.42(3) and 1.55(2) A for the tBu and cHex derivatives, respectively.

Modularly Designed Transition Metal PNP and PCP Pincer Complexes based on Aminophosphines: Synthesis and Catalytic Applications

Transition metal complexes are indispensable tools for any synthetic chemist. Ideally, any metal-mediated process should be fast, clean, efficient, and selective and take place in a catalytic manner. These criteria are especially important considering that many of the transition metals employed in catalysis are rare and expensive. One of the ways of modifying and controlling the properties of transition metal complexes is the use of appropriate ligand systems, such as pincer ligands. Usually consisting of a central aromatic backbone tethered to two two-electron donor groups by different spacers, this class of tridentate ligands have found numerous applications in various areas of chemistry, including catalysis, due to their combination of stability, activity, and variability. As we focused on pincer ligands featuring phosphines as donor groups, the lack of a general method for the preparation of both neutral (PNP) and anionic (PCP) pincer ligands using similar precursor compounds as well as the difficulty of introducing chirality into the structure of pincer ligands prompted us to investigate the use of amines as spacers between the aromatic ring and the phosphines. By introduction of aminophosphine and phosphoramidite moieties into their structure, the synthesis of both PNP and PCP ligands can be achieved via condensation reactions between aromatic diamines and electrophilic chlorophosphines (or chlorophosphites). Moreover, chiral pincer complexes can be easily obtained by using building blocks obtained from the chiral pool. Thus, we have developed a modular synthetic strategy with which the steric, electronic, and stereochemical properties of the ligands can be varied systematically. With the ligands in hand, we studied their reactivity towards different transition metal precursors, such as molybdenum, ruthenium, iron, nickel, palladium, and platinum. This has resulted in the preparation of a range of new pincer complexes, including various iron complexes, as well as the first heptacoordinated molybdenum pincer complexes and several pentacoordinated nickel complexes by using a controlled ligand decomposition pathway. In addition, we have investigated the use of some of the complexes as catalysts in different C-C coupling reactions: for example, the palladium PNP and PCP pincer complexes can be employed as catalysts in the well known Suzuki-Miyaura coupling, while the iron PNP complexes catalyze the coupling of aromatic aldehydes with ethyl diazoacetate under very mild reaction conditions to give selectively 3-hydroxyacrylates, which are otherwise difficult to prepare. While this Account presents an overview of current research on the chemistry of P-N bond containing pincer ligands and complexes, we believe that further investigations will give deeper insights into the reactivity and applicability of aminophosphine-based pincer complexes.

Ligand effects on the stability of the insertion products: A DFT study of oxidative addition of NH 3 to iridium(I) complex

The density functional theory (DFT) calculations were used to study the effects of PCP ancillary ligands on the relative stabilities of hydrido amido complexes and ammonia coordination complexes. Calculations on the four compounds 1a, 1b, 2a and 2b containing PCP ligands with t-butyl groups on P atoms showed that 1b is more stable than 1a and 2a is more stable than 2b. Calculations also showed that the relative energies of hydrido amido complexes with respect to the isomeric ammonia coordinated complexes vary with the different substituent groups (R = H, Me and t Bu) on the P atoms of the PCP ligands. An alternative method to study the ligand effects introduced by different substituents on the P atoms is to vary the nuclear charge on the P atoms of PCP ligand. The relative energies were predicted to decrease with the nuclear charge of the P atoms on the PCP ligands, which indicates that increasing the electron donating ability tend to favor the hydrido amido complexes over the ammonia coordination complexes: [Display omitted]

Synthesis and Structural Characterization of a Tetranuclear Zinc(II) Complex with P,P'-Diphenylmethylenediphosphinate (pcp) and 2,2'-Bipyridine (2,2'-bipy) Ligands

A new tetranuclear complex of zinc(II) with P,P′-diphenylmethylenediphosphinate and 2,2′- bipyridine ligands was synthesized. [(pcp)(2,2′-bipy)Zn (μ3-pcp)Zn (2,2′-bipy)]2 · 6H2O was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and X-ray diffractometry. The structure consists of tetranuclear complexes connected through water hydrogen-bonding interactions in corrugated 2D layers. Two crystallographically independent zinc ions are in a distorted five-coordinate environment, being surrounded by three oxygen atoms of phosphinate groups (from two pcp ligands) and by two bipy nitrogen donors. Of the two independent pcp anions the first one utilizes all of its oxygen donors to coordinate one metal as bidentate and two metal atoms as a monodentate ligand, whereas the second one is only bidentate for one metal atom.

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 (CF3PCPH) reacts at ambient temperatures with (cod)Pt(Me)Cl (cod = 1,5-cyclooctadiene) and (cod)PtMe2 to afford unmetalated PCPH-bridged products [(CF3PCPH)Pt(Me)Cl]x and cis-[(CF3PCPH)PtMe2]2, respectively. cis-[(CF3PCPH)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 (CF3PCP)PtCl and (CF3PCP)PtMe. Treatment of (CF3PCP)PtCl with MeMgBr provides an alternative route to (CF3PCP)PtMe. The carbonyl cation (CF3PCP)Pt(CO)+SbF6- (nu(CO) = 2143 cm(-1)) was readily prepared by chloride abstraction with AgSbF6 under 1 atm CO. nu(CO) data indicates that RfPCP ligands are electronically analogous to trans acceptor phosphine complexes such as trans-((C2F5)2PMe)2Pt(Me)(CO)+ (nu(CO) = 2149 cm-1).