The fluxional behaviour of [Pd(η2-tmetc)(NSMe)] (tmetc=tetramethylethylenetetracarboxylate, NSMe=2-methylthiomethylpyridine) in CD2Cl2 is governed by two mechanisms: (i) the concentration independent inversion at sulfur which averages the methylenic signals and collapses the four methyl signals of tmetc to two; (ii) the concentration dependent mechanism occurring via a dimeric intermediate with CS symmetry which collapses the two residual tmetc signals into a singlet. The fluxional behaviour of [Pd(η2-tmetc)(NSMe)] (tmetc=tetramethylethylenetetracarboxylate, NSMe=2-methylthiomethylpyridine) in CD2Cl2 is governed by two mechanisms: (1) the concentration independent inversion at sulfur; and (2) the concentration dependent mechanism occurring via a dimeric intermediate with CS symmetry.
The fluxional behaviour of [Pd(eta(2)-tmetc)(N-SMe) (tmetc = tetramethylethylenetetracarboxylate, N-SMe = 2-methylthiomethylpyridine) in CD2Cl2 is governed by two mechanisms: (i) the concentration independent inversion at sulfur which averages the methylenic signals and collapses the four methyl signals of tmetc to two; (ii) the concentration dependent mechanism occurring via a dimeric intermediate with C-s symmetry which collapses the two residual tmetc signals into a singlet. (C) 2002 Elsevier Science B.V. All rights reserved.
A novel mechanism for the fluxional behaviour of [Pd(η2-tetramethylethylenetetracarboxylate)(2-methylthiomethylpyridine)] / Canovese, Luciano; Lucchini, Vittorio; Santo, Claudio; Visentin, Fabiano; Zambon, Alfonso. - In: JOURNAL OF ORGANOMETALLIC CHEMISTRY. - ISSN 0022-328X. - 642:1-2(2002), pp. 58-63. [10.1016/S0022-328X(01)01197-4]
A novel mechanism for the fluxional behaviour of [Pd(η2-tetramethylethylenetetracarboxylate)(2-methylthiomethylpyridine)]
ZAMBON, Alfonso
2002
Abstract
The fluxional behaviour of [Pd(eta(2)-tmetc)(N-SMe) (tmetc = tetramethylethylenetetracarboxylate, N-SMe = 2-methylthiomethylpyridine) in CD2Cl2 is governed by two mechanisms: (i) the concentration independent inversion at sulfur which averages the methylenic signals and collapses the four methyl signals of tmetc to two; (ii) the concentration dependent mechanism occurring via a dimeric intermediate with C-s symmetry which collapses the two residual tmetc signals into a singlet. (C) 2002 Elsevier Science B.V. All rights reserved.
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