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Synthesis of the Stable Organopalladium(IV) Complexes [fac-PdRMe2(tripod)]X and Selective Reductive Elimination of Ethane from (eta-1-Allyl)palladium(IV) Complexes To Form (eta-3-Allyl)palladium(II) Complexes

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Brown, DG, Byers, PK and Canty, AJ 1990 , 'Synthesis of the Stable Organopalladium(IV) Complexes [fac-PdRMe2(tripod)]X and Selective Reductive Elimination of Ethane from (eta-1-Allyl)palladium(IV) Complexes To Form (eta-3-Allyl)palladium(II) Complexes' , Organometallics, vol. 9, no. 4 , pp. 1231-1235 , doi: 10.1021/om00118a052.

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Abstract

Oxidative addition of organo halides, RX, to dimethylpalladium(II) complexes, PdMe2(tripod), has led
to isolation of the first examples of ethyl-, n-propyl-, (eta-1-benzyl)-, and (eta-1-allyl)palladium(IV) complexes.
With the tripod ligand as bis(1-methylimidazol-2-yl)(pyridin-2-yl)methane,(py)(mim)2CH, the palladium(IV)
complexes occur as mixtures of isomers with R trans to py and mim groups in [fac-PdRMe,{(py)(mim)2CH-N,N',N'}]X. Tris(pyrazo1-1-y1)methane as a ligand gives unstable palladium(IV) complexes, with the benzyl and 2-propenyl complexes undergoing facile reductive elimination of ethane to form
organopalladium(II) products, including [PdI(eta-3-C3H5)]2, and the complex salt [Pd(eta-3-C3H5){(pz)3CH]]-
[PdBr2(eta-3-C3H5)]. Allyl exchange occurs for [Pd(ete-3-C3H5)(L)][PdBr2(eta-3-C3H5)] (L = (pz)3CH, (pz)2CMe2),
with (pz)3CH also exchanging coordinated and uncoordinated pz groups and with the cation [Pd(eta-3-C3H5){(pz)2CMe2}]+ present as two conformers in equilibrium.

Item Type: Article
Authors/Creators:Brown, DG and Byers, PK and Canty, AJ
Journal or Publication Title: Organometallics
ISSN: 0276-7333
DOI / ID Number: 10.1021/om00118a052
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