NDLI: A redox series of gallium(III) complexes: ligand -based two-electron oxidation affords a gallium–thiolate complex

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A redox series of gallium(III) complexes: ligand -based two-electron oxidation affords a gallium–thiolate complex

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Berben, Louise A. Kowolik, Kristin Shanmugam, Maheswaran Myers, Thomas W. Cates, Chelsea D.
Description	Author Affiliation: Kowolik K ( Department of Chemistry, University of California, Davis, CA 95616, USA.)
Abstract	We have prepared a series of gallium(III) complexes of the redox active iminopyridine ligand ( IP ). Reaction of $GaCl_{3}$ with iminopyridine ligand ( IP ) in the presence of either two or four equivalents of sodium metal resulted in the formation of deep green $(IP^{−})_{2}GaCl$ (1), or deep purple $[(DME)_{3}Na][(IP^{2−})_{2}Ga]$ (2a), respectively. Complex 1 is paramagnetic with a room temperature magnetic moment of 2.3 $μ_{B}$ which falls to 0.5 $μ_{B}$ at 5 K. These observations indicate that two ligand radicals comprise a triplet at room temperature which becomes a singlet due to antiferromagnetic coupling at low temperature. Complex 2 is diamagnetic. Cyclic voltammograms recorded on 0.3 M $Bu_{4}NPF_{6}$ THF solutions of $[Na(THF)_{6}][(IP^{2−})_{2}Ga]^{−}$ (2b) indicate that oxidation of 2b occurs in two two-electron steps at −1.31 V and −0.54 V vs. SCE . The observation of two-electron redox events indicates that electronic coupling through the gallium(III) center is minimal and that the two IP ligand on 2b are oxidized concurrently. Oxidation of 2 with one equivalent of MeS–SMe afforded the two-electron oxidized product $(IP^{−})_{2}Ga(SMe)$ (3). This complex has an electronic structure analogous to 1. Accordingly, both 1 and 3 are deep green in color and magnetic susceptibility measurements performed on 3 confirm the triplet character of the complex at room temperature. Electron paramagnetic resonance experiments on 1 and 3 display a quartet signal at g = 2.0 which confirmed the triplet nature of the compounds, and a half field signal consistent with the integer spin state.
ISSN	14779226
Issue Number	26
Journal	Dalton Trans.
Volume Number	41
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-07-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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