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Control of Reactivity of Dinuclear Nickel(II) Amine-Thiolate Complexes

✍ Scribed by Berthold Kersting

Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
494 KB
Volume
1999
Category
Article
ISSN
1434-1948

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✦ Synopsis

The coordination chemistry of a series of dinickel complexes and room temperature magnetic susceptibility measurements. Complexes 10, 11, or 12 readily add other co-of the new septadentate amine-thiolate ligand N, NЈ-bis[2thio-3-aminomethyl-5-tert-butylbenzyl]diethylenetriamine, ligands at the NiNЈ 3 S 2 L fragment by substitution of the solvent molecule L (10, 12) or the chloride substituent (11). H 2 9, has been investigated in the context of ligand binding and oxidation state changes. The complexes The overall structure of the parent complexes is not affected by the substitution reactions. An electrochemical study has [Ni 2 (9)(L)][ClO 4 ] 2 (10), [Ni 2 (9)(Cl)][Cl] (11), [Ni 2 (9)(L)][BPh 4 ] 2 (12), and [Ni 2 (9)(NCS)][OH•OH 2 ] (13) have central N 2 Ni(µ-shown that complex 10 undergoes two successive oneelectron oxidations at +0.88 and +0.41 V vs SCE. The oxidized SR) 2 NiNЈ 3 L cores [L = labile solvent molecule (10, 12), Cl - (11), and NCS -(13)] composed of dithiolate bridged planar species are not thermally stable, but electronic absorption spectra and EPR spectra are indicative of the presence of NiN 2 S 2 and six-coordinate NiNЈ 3 S 2 L units. This is demonstrated for 11 and 13 by crystal structure Ni III species. determinations and for 10 and 12 by UV/Vis spectroscopy [a] Institut für Anorganische und Analytische Chemie, Universität Freiburg, focused on the reactivity of nickel complexes of the amine-Albertstrasse 21, D-79104 Freiburg, Germany

thiolate ligand H 2 9 (see Scheme 2), which provides dissimi-

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