Sato Keita, Komuro Takashi, Imashuku Susumu, Li Hongyi, Ichitsubo Tetsu, Hashimoto Hisako
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan.
Inorg Chem. 2024 Sep 9;63(36):16940-16948. doi: 10.1021/acs.inorgchem.4c03356. Epub 2024 Aug 27.
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)(H)M←:AlH(NHC) (NHC = N-heterocyclic carbene, = 1 or 2), were synthesized in 43-63% yields by the one-step reaction of Cp*M(CO)(py)Me with HAl·NHC. The characterization included H and Al 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) 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 CO to CO were also demonstrated.
首次以碱稳定形式实现了具有母体Al(I)-H单元的过渡金属配合物的分离和表征。通过CpM(CO)(py)Me与HAl·NHC的一步反应，以43-63%的产率合成了W和Fe配合物Cp(CO)(H)M←:AlH(NHC)（NHC = N-杂环卡宾， = 1或2）。表征包括氢和铝核磁共振（NMR）以及红外（IR）光谱分析，还有密度泛函理论（DFT）计算，这些结果揭示了:AlH(NHC)配体极强的σ供电子能力以及高度极化的M(δ-)←:Al(δ+)配位键。这些配合物中Al中心的一价氧化态通过X射线光电子能谱（XPS）得到证实。还展示了碳二亚胺的氢化铝化反应以及将CO还原为CO的反应。
