ISSN:
1434-1948
Keywords:
Septadentate N5S2-ligand
;
Dinuclear complexes
;
Nickel
;
Reactivity
;
Redox chemistry
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The coordination chemistry of a series of dinickel complexes of the new septadentate amine-thiolate ligand N,N′-bis[2-thio-3-aminomethyl-5-tert-butylbenzyl]diethylenetriamine, H29, has been investigated in the context of ligand binding and oxidation state changes. The complexes [Ni2(9)(L)][ClO4]2 (10), [Ni2(9)(Cl)][Cl] (11), [Ni2(9)(L)][BPh4]2 (12), and [Ni2(9)(NCS)][OH·OH2] (13) have central N2Ni(μ-SR)2NiN′3L cores [L = labile solvent molecule (10, 12), Cl- (11), and NCS- (13)] composed of dithiolate bridged planar NiN2S2 and six-coordinate NiN′3S2L units. This is demonstrated for 11 and 13 by crystal structure determinations and for 10 and 12 by UV/Vis spectroscopy and room temperature magnetic susceptibility measurements. Complexes 10, 11, or 12 readily add other co-ligands at the NiN′3S2L fragment by substitution of the solvent molecule L (10, 12) or the chloride substituent (11). The overall structure of the parent complexes is not affected by the substitution reactions. An electrochemical study has shown that complex 10 undergoes two successive one-electron oxidations at +0.88 and +0.41 V vs SCE. The oxidized species are not thermally stable, but electronic absorption spectra and EPR spectra are indicative of the presence of NiIII species.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
