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

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

doi:10.1021/acs.inorgchem.4c05360

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

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

^*Corresponding author for this work

School of Engineering & Physical Sciences

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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.

Original language	English
Pages (from-to)	4043-4051
Number of pages	9
Journal	Inorganic Chemistry
Volume	64
Issue number	8
Early online date	19 Feb 2025
DOIs	https://doi.org/10.1021/acs.inorgchem.4c05360
Publication status	Published - 3 Mar 2025

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "ZnH2 as a Precursor to Catalytically Active Ru-ZnH Heterometallic Complexes",

abstract = "Reaction of [Ru(IPr)2(CO)H][BArF4] (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BArF4 = 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][BArF4] (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][BArF4] (7), and also proves to be catalytically active for the hydrogenation of 1-hexene and 5-hexene-2-one.",

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T1 - ZnH2 as a Precursor to Catalytically Active Ru-ZnH Heterometallic Complexes

AU - Pécharman, Anne-Frédérique

AU - Carpentier, Ambre

AU - Lowe, John P.

AU - Macgregor, Stuart A.

AU - Mahon, Mary F.

AU - Whittlesey, Michael K.

PY - 2025/3/3

Y1 - 2025/3/3

N2 - Reaction of [Ru(IPr)2(CO)H][BArF4] (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BArF4 = 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][BArF4] (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][BArF4] (7), and also proves to be catalytically active for the hydrogenation of 1-hexene and 5-hexene-2-one.

AB - Reaction of [Ru(IPr)2(CO)H][BArF4] (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BArF4 = 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][BArF4] (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][BArF4] (7), and also proves to be catalytically active for the hydrogenation of 1-hexene and 5-hexene-2-one.

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

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