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DOI: 10.1039/A805560B (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3765-3770

Platinum group metal complexes of a bis(diphenylphosphino)ethane ligand containing perfluoroalkyl ponytails

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Eric G. Hope, Raymond D. W. Kemmitt and Alison M. Stuart

Abstract

The perfluoroalkyl-derivatised bidentate phosphine (4-F13C6C6H4)2PCH2CH2P(C6H4C6F13-4)2 reacted with [PtCl2(MeCN)2], [PdCl2(MeCN)2] or [{RhCl(COD)}2] to yield the complexes [PtCl2(L–L)] 1, [PdCl2(L–L)] 2 and [Pd(L–L)2]2+2Cl– 3 or [{RhCl(L–L)}2] 5 respectively. Complex 3 was reduced with NaBH4 to [Pd(L–L)2] 4 and the chloride bridges in 5 were cleaved with triphenylphosphine to yield [RhCl(L–L)(PPh3)] 6. The reaction of the ligand with [{RhCl2(η5-C5Me5)}2] in a 1∶1 or a 2∶1 ratio yielded either [{RhCl2(η5-C5Me5)}2(L–L)] 7 or, after metathesis with NH4BF4 in acetone, [RhCl(η5-C5Me5)(L–L)]+BF4– 8 respectively. Throughout, spectroscopic studies indicated that the ligand co-ordinates in a similar fashion to bis(diphenylphosphino)ethane (dppe). Complex 7 and the analogous dppe complex are fluxional at room temperature. At the low temperature limit, all the nuclei within these molecules are chemically inequivalent for which simulation suggests a gauche-eclipsed conformation around the PCH2–CH2P bond. Solubility studies indicated that only 4 and 5 are preferentially soluble in perfluorocarbon solvents.

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