ZnH2 as a precursor to catalytically active Ru-ZnH heterometallic complexes

Anne-Frédérique Pecharman; Ambre Carpentier; John P. Lowe; Stuart MacGregor; Mary F Mahon; Michael Whittlesey

doi:10.1021/acs.inorgchem.4c05360

ZnH₂ as a precursor to catalytically active Ru-ZnH heterometallic complexes

Anne-Frédérique Pecharman, Ambre Carpentier, John P. Lowe, Stuart MacGregor, Mary F Mahon, Michael Whittlesey

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	4043-4051
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

Acknowledgements

We wish to thank Dr David Liptrot for access to ATR-IR spectroscopy and Professor Jun Okuda for sharing experimental data prior to publication.

Funding

We thank both the EPSRC (EP/T019743/1) and Heriot-Watt University (James Watt Scholarship to AC) for financial support

Funders	Funder number
Engineering and Physical Sciences Research Council	EP/T019743/1

Access to Document

10.1021/acs.inorgchem.4c05360Licence: CC BY

Cite this

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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 - Pecharman, Anne-Frédérique

AU - Carpentier, Ambre

AU - Lowe, John P.

AU - MacGregor, Stuart

AU - Mahon, Mary F

AU - Whittlesey, Michael

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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