Mechanistic Studies of Some Oxidative-addition Reactions: Free-radical Pathways in the Pt0-RX, Pt0-PhBr, and PtII-R'SO2X Reactions (R=Alkyl, R'=Aryl, X=Halide) and in the Related Rhodium(I) or Iridium(I) Systems

DOI: 10.1039/DT9800001448

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1448 - 1456 (1980)

Update date:2022-07-30

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Authors:

Hall, Thomas L.

Lappert, Michael F.

Lednor, Peter W.

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Article abstract of DOI:10.1039/DT9800001448

Spin-trapping studies, using R'NO (R'=Bu^t or C6HMe4-2,3,5,6), have been carried out on: (i) various Pt⁰-alkyl halide (RX) systems, e.g. (R''=Et or Ph, n=3 or 4)-Mel; (ii) a number of Pt^II-sulphonyl or acyl halide reactions, e.g. cis--p-MeC6H4SO2X; and (iii) several Rh^I- or Ir^I-alkyl halide additions.In most cases the appropriate nitroxyl spin adduct R(R')NO or R'(p-MeC6H4SO2)NO is observed by e.s.r. spectroscopy.In conjunction with appropriate control experiments, this leads to the unequivocal conclusion that free radicals are implicated in systems (i) (X= Cl, Br, or I) and (ii) (X= Cl or Br).By means of the nitrone PhCH=N(O)Bu^t, a platinum(I) complex has been trapped during the course of the -Etl reaction; its formulation as t)>I(PPh3)2> is based on e.s.r. data.Trityl chloride adds to a rhodium(I) or iridium(I) substrate> to give Ph3C and ; Ph2CHBr and give (Ph2CH)2 as the principal organic product.Galvinoxyl inhibits the addition of p-MeC6H4SO2Cl to .Azobis(isobutyronitrile) under photolysis catalyses the oxidative addition of PhBr to .Whereas the addition of MeI to in benzene leads exclusively to the 1:1 adduct, in tetrahydrofuran by far the major product is .It is concluded that reactive halides RX add to a platinum(0) substrate via a geminate radical pair IL_n(X)> + R, whereas with less reactive halides, or in the sulphonyl halide-Pt^II addition, a radical-chain mechanism is operative.

Full text of DOI:10.1039/DT9800001448

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