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Control of Reactivity of Dinuclear Nickel(II) Amine‐Thiolate Complexes
Author(s) -
Kersting Berthold
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199912)1999:12<2157::aid-ejic2157>3.0.co;2-h
Subject(s) - chemistry , electron paramagnetic resonance , substituent , diethylenetriamine , ligand (biochemistry) , nickel , reactivity (psychology) , molecule , amine gas treating , crystallography , context (archaeology) , coordination complex , thio , crystal structure , oxidation state , solvent , absorption spectroscopy , electrochemistry , stereochemistry , metal , organic chemistry , medicine , paleontology , physics , receptor , alternative medicine , electrode , nuclear magnetic resonance , pathology , biology , biochemistry , quantum mechanics
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, H 2 9 , has been investigated in the context of ligand binding and oxidation state changes. The complexes [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‐SR) 2 NiN′ 3 L cores [L = labile solvent molecule ( 10 , 12 ), Cl − ( 11 ), and NCS − ( 13 )] composed of dithiolate bridged planar NiN 2 S 2 and six‐coordinate NiN′ 3 S 2 L 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′ 3 S 2 L 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 Ni III species.