Abstract
The first isolation and characterization of transition metal complexes with the parent Al(I)-H unit were achieved in base-stabilized forms. W and Fe complexes, Cp*(CO)n(H)M←:AlH(NHC)2 (NHC = N-heterocyclic carbene, n = 1 or 2), were synthesized in 43-63% yields by the one-step reaction of Cp*M(CO)n(py)Me with H3Al·NHC. The characterization included 1H and 27Al nuclear magnetic resonance (NMR), and infrared (IR) spectroscopic analysis, as well as DFT calculations, which revealed the extremely strong σ-donating ability of the :AlH(NHC)2 ligand, and the highly polarized M(δ-)←:Al(δ+) coordination bonds. The monovalent oxidation state of the Al center of these complexes was confirmed by X-ray photoelectron spectroscopy (XPS). The hydroalumination of carbodiimide and the reduction of CO2 to CO were also demonstrated.
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