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Synthesis and coordination chemistry of ortho-perfluoroalkyl-derivatised triarylphosphines

By B. Croxtall, J. Fawcett, E. G. Hope and A. M. Stuart

Abstract

n order to establish the steric and electronic effects of fluorous ponytails in the ortho-positions of triarylphosphines the two novel phosphines, PPh2(2-C6H4C6F13) II and P(4-C6H4C6F13)2(2-C6H4C6F13) V, have been synthesised and their coordination chemistry investigated and compared with that of the ortho-trifluoromethyl-derivatised ligand, PPh2(2-C6H4CF3) VI. The single crystal X-ray structures of Ph2P(O)(2-C6H4C6F13) and Ph2P(O)(2-C6H4CF3), along with that of PPh2(2-C6H4CF3), are reported and compared with each other. The large steric influence of the ortho-trifluoromethyl and -perfluorohexyl substituents results in the formation of the, normally, less-thermodynamically favoured trans-[PtCl2L2] complexes. Analysis of the single crystal X-ray structures of trans-[PtCl2{PPh2(2-C6H4CF3)}2] 1, trans-[PtCl2{PPh2(2-C6H4C6F13)}2] 2 and trans-[RhCl(CO){PPh2(2-C6H4CF3)}2] 4 reveals a larger cone angle for PPh2(2-C6H4CF3) (169°) than for PPh2(2-C6H4C6F13). An average cone angle of 166° was calculated for the latter phosphine with values ranging from 164 to 168°

Year: 2002
DOI identifier: 10.1039/b107390g
OAI identifier: oai:lra.le.ac.uk:2381/637
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