Publication history Received28 February 2011Published online13 may 2011Published inissue 8 June 2011

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Electrophilic activation and also subsequent palliation of substrates is in basic not feasible because very Lewis acidic steels lack accessibility to multiple oxidization states. Herein, we show that transition metal-like oxidization processes and electronic structure and also magnetic properties have the right to be imparted come aluminum(III). Bis(iminopyridine) complexes comprise neutral, monoanionic, and also dianionic iminopyridine ligands (IP) have actually been characterized structurally and electronically; yellow (IP)AlCl3 (1), deep eco-friendly (IP–)2AlCl (2) and also (IP–)2Al(CF3SO3) (3), and deep violet <(IP2–)Al>− (5) are presented. The mixed-valent, monoradical complicated (IP–)(IP2–)Al is unstable toward C–C coupling, and also <(IP2–)Al>2−(μ-IP–IP)2– (4) has been isolated. Variable-temperature magnetic susceptibility and EPR spectroscopy measurements indicate that the biradical personality of the ligand-based triplet in 2 is stabilized by strong antiferromagnetic exchange coupling mediated by aluminum(III): J = −230 cm–1 because that Ĥ = −2J(ŜL(1)·ŜL(2)). Coordination geometry-dependent (IP–)–(IP–) interaction through aluminum(III) is it was observed electrochemically. The cyclic voltammogram the trigonal bipyramidal 2 display screens successive ligand-based oxidation occasions for the two IP1–/0 processes, at −0.86 and −1.20 V vs SCE. The 0.34 V spacing between redox couples synchronizes to a conproportionation continuous of Kc = 105.8 because that the procedure (IP–)2AlCl + (IP)2AlCl → 2(IP–)(IP)AlCl regular with Robin and Day class II mixed-valent behavior. Tetrahedral 5 display screens localized, class I behavior as indicated by closely spaced oxidization couples. Furthermore, CV’s of 2 and also 5 indicate that changes in the coordination environment of the aluminum center shift the potentials for the IP1–/0 and IP2–/1– oxidation couples by up to 0.9 V.

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CIF records for the structures of 16, and also UV–visible spectra of IP and also 4. Depictions of the solid-state structures of 1, 3, and 6. Cyclic voltammogram for IP, magnetic susceptibility data because that 4 and 5, and fits come variable-temperature EPR data because that 2. This product is available cost-free of fee via the internet at

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