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Electrochemical reduction of the bis(1,2,6,7-tetracyano-3,5-dihydro-3,5-diimino-pyrrolizinido) palladium (II) complex: syntheses and properties of its radical monoanion as the tetraethylammonium salt

The electrochemical reduction of the bis(1,2,67-tetracyano-3,5-dihydro-3,5-diiminopyrrolizinido) palladium(II) complex, Pd(C 11N 7H 2) 2, furnishes the corresponding radical anion, isolated as PdL 2·NEt 4·2CH 3CN·2H 2O ( 1). 1 is a semiconductor of low conductivity ( σ RT = 1.4 × 10 −10 S cm −1), pr...

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Bibliographic Details
Published in:Inorganica Chimica Acta 1996-06, Vol.247 (1), p.75-78
Main Authors: Flamini, Alberto, Poli, Nicola, Panusa, Alessia
Format: Article
Language:English
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Summary:The electrochemical reduction of the bis(1,2,67-tetracyano-3,5-dihydro-3,5-diiminopyrrolizinido) palladium(II) complex, Pd(C 11N 7H 2) 2, furnishes the corresponding radical anion, isolated as PdL 2·NEt 4·2CH 3CN·2H 2O ( 1). 1 is a semiconductor of low conductivity ( σ RT = 1.4 × 10 −10 S cm −1), presumably consisting of segregated stacks of radical anions, weakly interacting antiferromagnetically at room temperature ( μ SO = 1.50 μ B, 300 K). Lowering the temperature, the magnetic moment undergoes a gradual reduction ( μ SO = 0.65 μ B, 5 K), due probably to a partial dimerisation of the radical units. Other chemicophysical properties of 1 are in agreement with its proposed solid state structure: (i) the EPR signal is strong and broad ( g = 2.005, linewidth = 19G), indicative of a high spin concentration fast relaxing along the anion stacks; (ii) the reflectance spectrum shows a broad band centred at 1200 nm, due to an interanionic π→π ∗ transition between adjacent radical anions, delocalised along the anion stacks.
ISSN:0020-1693
1873-3255
DOI:10.1016/0020-1693(95)04831-6