Complexes of group 13 metal (Al, Ga, In) ions with neutral α-diimine ligands have been prepared and characterized. The Al(III) and Ga(III) [M(α-diimine)2Cl2][MCl4] complexes catalyze the epoxidation of alkenes by peracetic acid under ambient conditions. The two complexes display nearly identical reactivity, demonstrating that inexpensive and highly abundant aluminum is a viable catalytic metal for these reactions.
The synthesis and full characterization of a series of neutral ligand α-diimine complexes of aluminum are reported. The compounds [Al(L)Cl)][AlCl] [L = N, N'-bis(4-R-CH)-2,3-dimethyl-1,4-diazabutadiene] are structurally analogous, as determined by multinuclear NMR spectroscopy and solid-state X-ray diffraction, across a range of electron-donating [R = Me (2), Bu (3), OMe (4), and NMe (5)] and electron-withdrawing [R = Cl (6), CF (7), and NO (8)] substituents in the aryl side arm of the ligand. UV-vis absorption spectroscopy and electrochemistry were used to access the optical and electrochemical properties, respectively, of the complexes. Both sets of properties are shown to be dependent on the R substituent. Density functional theory calculations performed on the [Al(L)Cl)][AlCl] complex (1) indicate primarily ligand-based frontier orbitals and were used to help support our discussion of both the spectral and electrochemical data. We also report the reaction of the L ligand with both AlBr and AlI and demonstrate a different reactivity profile for the heavier halide relative to the lighter members of the group.
We report a co-electrocatalytic system for the selective reduction of CO2 to CO, comprised of a previously reported molecular Cr complex and 5-phenylbenzo[b]phosphindole-5-oxide (PhBPO) as a redox mediator. Under protic...
A series of Ca-Mn clusters with the ligand 2-pyridinemethoxide (Py-CH2O) have been prepared with varying degrees of topological similarity to the biological oxygen-evolving complex. These clusters activate water as a...
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