ZnH2 as a Precursor to Catalytically Active Ru–ZnH Heterometallic Complexes

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-02-19 DOI:10.1021/acs.inorgchem.4c05360

Anne-Frédérique Pécharman, Ambre Carpentier, John P. Lowe, Stuart A. Macgregor, Mary F. Mahon, Michael K. Whittlesey

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引用次数: 0

Abstract

Reaction of [Ru(IPr)₂(CO)H][BAr^F₄] (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BAr^F₄ = B{3,5(CF₃)₂C₆H₃}₄) with an excess of ZnH₂ in THF gives the structurally characterized neutral Ru(ZnH) complex [Ru(IPr)₂(CO)(ZnH)H₃] (6) and Ru(ZnH)₂ salt [Ru(IPr)₂(CO)(ZnH)₂H₃][BAr^F₄] (5). Crystallographic and computational analyses show the presence of both bridging Ru–H–Zn hydrides and terminal Ru-hydrides in the two products. Calculations also identify a low-energy H/ZnH exchange pathway that rationalizes the experimentally observed (EXSY) fluxionality of the hydrides in 5. At room temperature, this compound undergoes stoichiometric exchange with ZnMe₂ to give [Ru(IPr)₂(CO)(ZnMe)₂H₃][BAr^F₄] (7), and also proves to be catalytically active for the hydrogenation of 1-hexene and 5-hexene-2-one.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.