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Oxidation of Diorganopalladium(II) Complexes by Water and Halogens: Reactions Involving Methyl Group Transfer and Structural Studies of Hydrogen-Bonded Adducts Formed by Aryl Alcohols with the Pallada(IV)cyclopentane Complex Pd(CH2CH2CH2CH2)(OH){(pz)(3)BH}([(pz)(3)BH](-)=tris(pyrazol-1-yl)borate)

Citation

Canty, AJ and Jin, H and Roberts, AJ and Skelton, BW and White, AH, Oxidation of Diorganopalladium(II) Complexes by Water and Halogens: Reactions Involving Methyl Group Transfer and Structural Studies of Hydrogen-Bonded Adducts Formed by Aryl Alcohols with the Pallada(IV)cyclopentane Complex Pd(CH2CH2CH2CH2)(OH){(pz)(3)BH}([(pz)(3)BH](-)=tris(pyrazol-1-yl)borate), Organometallics, 15, (26) pp. 5713-5722. ISSN 0276-7333 (1996) [Refereed Article]

DOI: doi:10.1021/om960583e

Abstract

The first observations of oxidation of palladium(II) by water are reported. The pallada-(II)cyclic complex ion [Pd(CH 2CH 2CH 2CH 2){(pz) 3BH}] - [(pz) 3BH = tris (pyrazol-1-yl)borate)] is oxidized by water in acetone or tetrahydrofuran to form Pd(CH 2CH 2CH 2CH 2)(OH){(pz) 3-BH} and hydrogen, and oxidation by hydrogen peroxide gives the same complex. Oxidation by halogens results in the formation of Pd(CH 2CH 2CH 2CH 2)(X){(pz) 3BH} (X = Cl, Br, I), and these complexes, together with the hydroxopalladium(IV) complex, represent the first examples of stable dihydrocarbylpalladium(IV) complexes. The octahedral complex Pd(CH 2CH 2CH 2CH 2)(OH){(pz) 3BH} forms adducts with phenol, 3-methylphenol, and pentafluorophenol with an overall composition of Pd(CH 2CH 2CH 2CH 2)(OH){(pz) 3BH}·2ArOH (5 and 6) and Pd(CH 2CH 2CH 2CH 2)(OH){(pz) 3BH}·C 6F 5OH (7). Complex hydrogen-bonding interactions occur in the adducts, consistent with the assignment of the phenol and 3-methylphenol adducts as hydroxopalladium(IV) complexes and the pentafluorophenol adduct as an aquapalladium(IV) complex. Complexes 5 and 6 are considered to contain the hydrogen-bonding motifs H-O(Pd)⋯HO(Ph)⋯HOPh and Ar(H)O⋯H-O(Pd)⋯HOAr, respectively, and 7 to contain an aquapalladium(IV) cation in which both hydrogen atoms of the aqua ligand act as hydrogen-bond donors to pentafluorophenoxide ions in a centro-symmetric dimer, [Pd(CH 2CH 2CH 2CH 2)(OH 2){(pz) 3BH}·C 6F 5O] 2. The complex ions [PdMeR{(pz) 3BH}] - (R = Me, Ph) react with water or halogens to form the PdMe 2R{(pz) 3- BH} and Pd IIR species, and in the case of water as the oxidant, hydrogen is also formed. These reactions occur via initial oxidation to form undetected palladium(IV) species, presumably PdMeR(X){(pz) 3BH} (X = OH, Cl, Br, I), which undergo rapid methyl group exchange reactions with [PdMeR{(pz) 3BH}] - to form Pd IIR species and PdMe 2R{(pz) 3BH}. The oxidation of palladium(II) by water and the structural analysis of hydroxo- and aquapalladium(IV) complexes represent the first examples of organopalladium(IV) chemistry in aqueous media.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Canty, AJ (Professor Allan Canty)
Author:Jin, H (Dr Hong Jin)
Author:Roberts, AJ (Mr Alistair Roberts)
ID Code:8099
Year Published:1996
Web of Science® Times Cited:58
Deposited By:Chemistry
Deposited On:1996-08-01
Last Modified:2007-09-07
Downloads:0

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