The synthesis of three new [Pd(κ2-PP)MeCl] (PP = 1,1'-bis(dicylohexylphosphino)ferrocene (dcpf), 1-diphenylphosphino-1'-ditert-butylphosphinoferrocene (dppdtbpf) or 1,1’-bis(5-methyl-2-furanylphosphino)ferrocene (dfurpf)) compounds is described. The compounds were thoroughly characterized by NMR spectroscopy. The palladium center is approximately square planar, making the phosphine groups inequivalent. The cis/trans- of the Me and Cl ligands to the -PPh2 and PtBu2 groups for the dppdtbpf compound was determined from the X-ray crystal structure of [Pd(dppdtbpf)MeCl]. The oxidative electrochemistry of the three new compounds as well as that of the reported [Pd(κ2-PP)MeCl] (PP = 1,1'-bis(diphenylphosphino)ferrocene (dppf), or 1,1'-bis(diiso-propylphosphino)ferrocene (dippf)) and [Pd(κ3-dtbpf)Me]Cl (dtbpf = 1,1'- bis(ditert-butylphosphino)ferrocene) was examined. Unlike the related [Pd(PP)Cl2] compounds, oxidation of the [Pd(PP)MeCl] compounds typically displayed multiple irreversible waves. The reaction of the compounds with κ2-bis(phosphino)ferrocene ligands with sodium tetrakis(3,5-bis(trifluoromethyl)phenylborate) Na[BArF24] resulted in the loss of a chloride ligand. The catalytic activity of the resulting compounds was examined for the polymerization of phenylacetylene.

Synthesis, characterization and electrochemistry of [Pd(PP)MeCl] (PP = bis(phosphino)ferrocene) compounds

ACS Spring Meeting 2021

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