Paul, Parimal ; Chakladar, Sukla ; Nag, Kamalaksha (1990) Stereochemical aspects of the cycloaddition reaction products of the coordinated azide in palladium complexes [Pd(N---N---S)(N3)] Inorganica Chimica Acta, 170 (1). pp. 27-35. ISSN 0020-1693
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Official URL: http://linkinghub.elsevier.com/retrieve/pii/S00201...
Related URL: http://dx.doi.org/10.1016/S0020-1693(00)80405-3
Abstract
Cycloaddition reactions of coordinated azide in the palladium(II) complexes [PdL(N3)] (L=L1---L3; HL1 = methyl 2-(2-aminoethyl)amino)cyclopent-1-enedithiocarboxylate, HL2 = methyl 2-((2-dimethylamino)ethyl)amino)cyclopent-1-enedithiocarboxylate, HL3 = methyl 2-((2-diethylamino)ethyl)amino)cyclopent-1-enedithiocarboxylate)) with nitriles, alkynes, alkenes, PhNCS and CS2 have been investigated. In all the cases the products obtained are of the type [PdL-(heterocycle)-]. The tetrazolates obtained by reacting [PdL(N3)] with nitriles give rise to syn-N(1)-, anti-N(1)- and N(2)-bound isomers, whose relative abundances have been determined from 1H NMR spectra. The relative abundance of the N(2)-bound species increases with electron-withdrawing substituents on the tetrazolates. The triazolato and triazolinato complexes obtained from alkynes and alkenes, repectively exist only as the N(2) isomer. The rate constants for the reaction of [PdL(N3)] with aromatic nitriles show a strong dependence on σp (Hammett parameters) of the substituent. The reaction rate also depends upon the steric influences of the substituents attached to the terminal nitrogen atom of L and decreases in the order: [PdL1(N3)]> [PdL2(N3)]>[PdL3(N3)].
Item Type: | Article |
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ID Code: | 22745 |
Deposited On: | 24 Nov 2010 07:56 |
Last Modified: | 23 Jan 2011 16:14 |
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