ISSN:
1434-1948
Keywords:
Dinuclear complexes
;
Nickel
;
Palladium
;
Amine-thiolate ligands
;
Amine-selenolate ligands
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The preparation and characterization of dinuclear NiII and PdII complexes of the tridentate amine-chalcogenolate ligands 4-tert-butyl-2,6-di(aminomethyl)thiophenol (4a) and 4-tert-butyl-2,6-di(aminomethyl)selenophenol (4b) are re-ported. Reaction of 4a,b with Ni(ClO4)2·6 H2O or (COD)PdCl2 in a 1:1 molar ratio yields 1:1 complexes of composition [M2(L)2][BPh4]2·CH3CN·CH3OH [M = Ni, L = 4a,b (5a,b); M = Pd, L = 4a,b (6a,b)]. The palladium complex 6a is isomorphous with 5a as shown by X-ray crystal structure analysis. NMR studies reveal that both complexes retain their solid-state structure in solution and that the selenolate complexes are isostructural with the thiolate complexes. All complexes undergo electrochemically reversible one-electron transfer processes in the potential range -1.0 to -0.8 V vs. SCE ascribed to metal-centered reductions with formation of mixed-valent MI,II species [M2(L)2]+. Further reduction at more negative potentials then leads to the neutral [M2(L)2] species, which are not stable on the time scale of the CV experiment. The spectroscopic properties of the thiolate and selenolate complexes are very similar indicating electronically similar properties of the tridentate amine-chalcogenolate ligands.
Type of Medium:
Electronic Resource