Reactions of low-valent metal complexes with fluorocarbons. Part 31. Bis(η-cyclo-octa-1,5-diene)-platinum and -palladium, with fluoroolefins
- 1 January 1977
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 10,p. 1010-1016
- https://doi.org/10.1039/dt9770001010
Abstract
Reaction of bis(η-cyclo-octa-1,5-diene)platinum with C2F4 gives an octafluorodiplatinacyclohexane complex [Pt2(µ-CF2·CF2)2(1,5-C8H12)2], which undergoes ligand-displacement reactions to form [Pt2(µ-CF2·CF2)2L4][L = PEt3; L2= 1,2-C6H4(AsMe2)2]. Tris(η-bicyclo[2.2.1]heptene)platinum reacts with C2F4 to give the mononuclear species [[graphic omitted]F2)(C7H10)2], which with P(OMe)3 and with 1,5-C8H12 forms, respectively, [[graphic omitted]F2){P(OMe)3}2] and [Pt2(µ-CF2·CF2)2(1,5-C8H12)2]. In contrast, [Pd(1,5-C8H12)2] and C2F4 afford the four-ring system [(1,5-C8H12)[graphic omitted]d(1,5-C8H12)]. Chlorotrifluoroethylene undergoes a vinyl-rearrangement reaction on treatment with [Pt(1,5-C8H12)2] yielding [PtCl(CF:CF2)(1,5-C8H12)]. Hexafluoropropene rearranges on treatment with [M(1,5-C8H12)2](M = Pt or Pd) to form [(1,5-C8H12)[graphic omitted](1,5-C8H12)]. In the case of the palladium system, the complex [[graphic omitted]F(CF3)}(1,5-C8H12)] has also been isolated, and shown to be the precursor of the binuclear complex. Octafluorobut-2-ene, hexafluoroacetone, and 1,1-dicyano-2,2-bis(trifluoromethyl)ethylene react with [Pd(1,5-C8H12)2] to give the conventional products [[graphic omitted]F(CF3)}(1,5-C8H12)], [[graphic omitted]}(1,5-C8H12)], and [[graphic omitted](CF3)2}(1,5-C8H12)].Keywords
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