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N.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, 119991, Leninsky avenue, 31, Moscow, Russian Federation
; Fax: +007 495 9541279
; Tel: +007 495 9554844
A.A. Baikov Institute of Metallurgy and Material Science of Russian Academy of Sciences, 119991, Leninsky avenue, 49, Moscow, Russian Federation
; Fax: +007 495 1358680
; Tel: +007 495 7181655
Dalton Trans., 2013,42, 3712-3720
10 Oct 2012,
10 Dec 2012
First published online
11 Dec 2012
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(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(N)OC(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–.
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