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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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Published in: | Inorganica Chimica Acta 1996-06, Vol.247 (1), p.75-78 |
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Main Authors: | , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites |
Online Access: | Get full text |
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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. |
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ISSN: | 0020-1693 1873-3255 |
DOI: | 10.1016/0020-1693(95)04831-6 |