Highly fluorous complexes of nickel, palladium and platinum: solubility and catalysis in high pressure CO2

Abstract

A variety of Group 10 metal complexes [MXY(dfppp)], M = Ni, X, Y = Cl, Br, M = Pd, Pt, X, Y = Cl or CH(3), containing the recently reported highly fluorous diphosphine ligand, dfppp, 1,3-bis[di(fluoroponytail)phosphino]propane, {(p-F(13)C(6)C(6)H(4))(2)P}(2)(CH(2))(3) have been synthesised. They have been characterised by NMR, mass spectrometry and microanalysis, with two platinum complexes, [PtCl(2)(dfppp)] and [PtClMe(dfppp)], structurally characterised by single crystal X-ray diffraction studies. The highly fluorous nature of the ligands affords the complexes good supercritical CO(2) solubility as measured by supercritical fluid extraction (SFE), and has allowed for the copolymerisation of CO and ethylene using [PdClMe(dfppp)] as the catalyst precursor and CO(2) as the solvent. Additionally, PtCl(2) complexes of the new ligands dfppb, {(p-F(13)C(6)C(6)H(4))(2)P}(2)(CH(2))(4), and dfpop, {(p-F(13)C(6)C(6)H(4)O)(2)P}(2)(CH(2))(3), have also been prepared and characterised.

Organophosphines in Cis-PtP2CCl Derivatives Structural Aspects

“…In another twenty five complexes: [40] In nine complexes: [46], and [Pt{η 2 -Ph2P(η 2 -C10H14N6)PPh2}(Me)(Cl)]hexane [47] each chelating-P,P ligand creates a six-membered metallocyclic ring with values of the P-Pt-P bite angles of 94° (PC3P) [29,[43][44][45][46] and 91.5° (PCNCP) [47].…”

Fluorous Organometallic Chemistry

“…The only examples of metal carbonyl clusters derivatised with fluorous ligands were reported in 2010 [66]. [Os 3 (CO) 11 [75].…”