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

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

^*Corresponding author for this work

School of Chemistry

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

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

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© 2025 The Authors. This article is licensed under CC-BY 4.0 (https://creativecommons.org/licenses/by/4.0/).
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CCDC 2368511 & 2368512: Experimental Crystal Structure Determination
Pécharman, A.-F. (Creator), Carpentier, A. (Creator), Lowe, J. P. (Creator), Macgregor, S. A. (Creator), Mahon, M. F. (Creator) & Whittlesey, M. K. (Creator), Cambridge Crystallographic Data Centre, 2025
DOI: 10.5517/ccdc.csd.cc2khml9, https://dx.doi.org/10.5517/ccdc.csd.cc2khmmb
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@article{6ed85e68d5de4a70acfe7fd56f601720,

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.",

author = "Anne-Frederique Pecharman and Ambre Carpentier and Lowe, {John P.} and Macgregor, {Stuart A.} and Mahon, {Mary F.} and Whittlesey, {Michael K.}",

note = "Funding: The authors thank both the EPSRC (EP/T019743/1) and Heriot-Watt University (James Watt Scholarship to AC) for financial support.",

year = "2025",

month = mar,

day = "3",

doi = "10.1021/acs.inorgchem.4c05360",

language = "English",

volume = "64",

pages = "4043--4051",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society (ACS)",

number = "8",

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TY - JOUR

T1 - ZnH2 as a precursor to catalytically active Ru–ZnH heterometallic complexes

AU - Pecharman, Anne-Frederique

AU - Carpentier, Ambre

AU - Lowe, John P.

AU - Macgregor, Stuart A.

AU - Mahon, Mary F.

AU - Whittlesey, Michael K.

N1 - Funding: The authors thank both the EPSRC (EP/T019743/1) and Heriot-Watt University (James Watt Scholarship to AC) for financial support.

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.

U2 - 10.1021/acs.inorgchem.4c05360

DO - 10.1021/acs.inorgchem.4c05360

M3 - Article

C2 - 39970375

SN - 0020-1669

VL - 64

SP - 4043

EP - 4051

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 8

ER -

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

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CCDC 2368511 & 2368512: Experimental Crystal Structure Determination

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