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Issue 10, 2013
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Reactivity of polynuclear palladium carboxylate complexes towards acetonitrile: synthesis and X-ray study of Pd2(C6H4-o-C([double bond, length as m-dash]NH)CH3)2(CH3CO2)2 and Pd5(CH3C([double bond, length as m-dash]N)OC([double bond, length as m-dash]N)CH3)(NO)(NO2)x(RCO2)7−x

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Abstract

Reactions of the polynuclear palladium carboxylate complexes (binary palladium carboxylates and palladium nitrosyl carboxylates) with acetonitrile in some common organic solvents are described. It was found that reaction of palladium acetate Pd3(μ-CH3CO2)6 with acetonitrile and benzene leads to the formation of a binuclear complex Pd2(C6H4-o-C([double bond, length as m-dash]NH)CH3)2(CH3CO2)2 containing molecules of orthometallated 1-phenylethanimine formed as a result of C–C-coupling of acetonitrile and benzene. Nitrosyl carboxylate complexes Pd4(NO)2(RCO2)6 promote more complicated transformations of acetonitrile that leads to the formation of coordinated acetimidic anhydride, which was found in Pd5(CH3C([double bond, length as m-dash]N)OC([double bond, length as m-dash]N)CH3)(NO)(NO2)x(RCO2)7−x clusters. Structures of all the complexes contained products of acetonitrile transformations and a new palladium nitrosyl carboxylate Pd4(NO)2(cyclo-C6H11CO2)6 was studied with XRD. Analysis of the structures allowed finding a “building block” of palladium nitrosyl carboxylate clusters, that is a 4-nuclear metal chain –Pd(μ-RCO2)2Pd(μ-NO)(μ-RCO2)Pd(μ-RCO2)2Pd–.

Graphical abstract: Reactivity of polynuclear palladium carboxylate complexes towards acetonitrile: synthesis and X-ray study of Pd2(C6H4-o-C( [[double bond, length as m-dash]] NH)CH3)2(CH3CO2)2 and Pd5(CH3C( [[double bond, length as m-dash]] N)OC( [[double bond, length as m-dash]] N)CH3)(NO)(NO2)x(RCO2)7−x

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Publication details

The article was received on 10 Oct 2012, accepted on 10 Dec 2012 and first published on 11 Dec 2012


Article type: Paper
DOI: 10.1039/C2DT32407E
Citation: Dalton Trans., 2013,42, 3712-3720
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    Reactivity of polynuclear palladium carboxylate complexes towards acetonitrile: synthesis and X-ray study of Pd2(C6H4-o-C([double bond, length as m-dash]NH)CH3)2(CH3CO2)2 and Pd5(CH3C([double bond, length as m-dash]N)OC([double bond, length as m-dash]N)CH3)(NO)(NO2)x(RCO2)7−x

    O. N. Shishilov, N. S. Akhmadullina, Y. N. Rezinkova, R. E. Podobedov, A. V. Churakov and I. A. Efimenko, Dalton Trans., 2013, 42, 3712
    DOI: 10.1039/C2DT32407E

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