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Inorg Chem. 2012 Nov 5;51(21):11891-7. doi: 10.1021/ic301792w. Epub 2012 Oct 23.

(IP)2Ga(III) complexes facilitate net two-electron redox transformations (IP = α-iminopyridine).

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Department of Chemistry, University of California-Davis, Davis, California 95616, USA.


Reaction of M(+)[(IP(2-))(2)Ga](-) (IP = iminopyridine, M = Bu(4)N, 1a; (DME)(3)Na, 1b) with pyridine N-oxide affords two-electron-oxidized (IP(-))(2)Ga(OH) (2) in reactions where the product outcome is independent of the cation identity, M(+). In a second example of net two-electron chemistry, outer sphere oxidation of M(+)[(IP(2-))(2)Ga](-) using either 1 or 2 equiv of the one-electron oxidant ferrocenium afforded [(IP(-))(2)Ga](+) (3) in either 44 or 87% yield, respectively. Reaction with 1 equiv of TEMPO, a one-electron oxidant, afforded the two-electron-oxidized product (IP(-))(2)Ga(TEMPO) (4). Reduction of 2IP by 3Na and subsequent reaction with GaCl(3) yielded a 1:1 mixture of (IP(-))(2)GaCl and 1. Most remarkably, all of these reactions are overall two-electron processes and only the (IP(-))(2)GaX and [(IP(2-))(2)Ga](-) oxidation states are thermodynamically accessible to us. Analogous aluminum chemistry previously afforded either one-electron or two-electron reactions and mixed-valent states. The thermodynamic accessibility of the mixed-valent states of (IP(2-))(IP(-))E, where E = Al or Ga, can be compared using cyclic voltammetry measurements. These measurements indicated that the mixed-valent state [(IP(2-))(IP(-))Ga](+) is not significantly stabilized with respect to disproportionation on the time scale of the electrochemistry experiment. The electrochemically observed differences in thermodynamic stability of the mixed-valent state [(IP(2-))(IP(-))E](+) can be rationalized by the observation that the dihedral angle between the ligand planes containing the π-system of IP is roughly 5° larger in all gallium complexes compared with aluminum analogs. Presumably, a larger dihedral angle provides weaker electronic coupling between the π-systems of IP via the E-X σ* orbital. Alternatively, the observed difference may be a result of the "inert pair effect": a contracted Ga component in the E-X σ* orbital would also afford weaker electronic coupling.


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