Transition Metal Parent Alumylene Complexes: Synthesis, Structures, and XPS Characterization of Aluminum Oxidation State.

Autor: Sato K; Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan., Komuro T; Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan., Imashuku S; Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan., Li H; Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan., Ichitsubo T; Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan., Hashimoto H; Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
Jazyk: angličtina
Zdroj: Inorganic chemistry [Inorg Chem] 2024 Sep 09; Vol. 63 (36), pp. 16940-16948. Date of Electronic Publication: 2024 Aug 27.
DOI: 10.1021/acs.inorgchem.4c03356
Abstrakt: 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 H 3 Al·NHC. The characterization included 1 H and 27 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) 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 CO 2 to CO were also demonstrated.
Databáze: MEDLINE