Anne-Frédérique Pécharman, Ambre Carpentier, John P. Lowe, Stuart A. Macgregor*, Mary F. Mahon* and Michael K. Whittlesey*,
{"title":"ZnH2作为催化活性Ru-ZnH异质金属配合物的前体","authors":"Anne-Frédérique Pécharman, Ambre Carpentier, John P. Lowe, Stuart A. Macgregor*, Mary F. Mahon* and Michael K. Whittlesey*, ","doi":"10.1021/acs.inorgchem.4c0536010.1021/acs.inorgchem.4c05360","DOIUrl":null,"url":null,"abstract":"<p >Reaction of [Ru(IPr)<sub>2</sub>(CO)H][BAr<sup>F</sup><sub>4</sub>] (<b>1</b>; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BAr<sup>F</sup><sub>4</sub> = B{3,5(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}<sub>4</sub>) with an excess of ZnH<sub>2</sub> in THF gives the structurally characterized neutral Ru(ZnH) complex [Ru(IPr)<sub>2</sub>(CO)(ZnH)H<sub>3</sub>] (<b>6</b>) and Ru(ZnH)<sub>2</sub> salt [Ru(IPr)<sub>2</sub>(CO)(ZnH)<sub>2</sub>H<sub>3</sub>][BAr<sup>F</sup><sub>4</sub>] (<b>5</b>). 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 <b>5</b>. At room temperature, this compound undergoes stoichiometric exchange with ZnMe<sub>2</sub> to give [Ru(IPr)<sub>2</sub>(CO)(ZnMe)<sub>2</sub>H<sub>3</sub>][BAr<sup>F</sup><sub>4</sub>] (<b>7</b>), and also proves to be catalytically active for the hydrogenation of 1-hexene and 5-hexene-2-one.</p><p >Zinc dihydride reacts with [Ru(IPr)<sub>2</sub>(CO)H][BAr<sup>F</sup><sub>4</sub>] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BAr<sup>F</sup><sub>4</sub> = B{C<sub>6</sub>H<sub>3</sub>(3,5-CF<sub>3</sub>)<sub>3</sub>}<sub>4</sub>) to afford the heterometallic ZnH-containing compounds [Ru(IPr)<sub>2</sub>(CO)(ZnH)<sub>2</sub>H<sub>3</sub>][BAr<sup>F</sup><sub>4</sub>] and [Ru(IPr)<sub>2</sub>(CO)(ZnH)H<sub>3</sub>]. Experiments and calculations have been used to probe the solution fluxionality and ZnH/ZnMe exchange of the former, which also proves to be catalytically active for alkene hydrogenation.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 8","pages":"4043–4051 4043–4051"},"PeriodicalIF":4.7000,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.inorgchem.4c05360","citationCount":"0","resultStr":"{\"title\":\"ZnH2 as a Precursor to Catalytically Active Ru–ZnH Heterometallic Complexes\",\"authors\":\"Anne-Frédérique Pécharman, Ambre Carpentier, John P. Lowe, Stuart A. Macgregor*, Mary F. Mahon* and Michael K. Whittlesey*, \",\"doi\":\"10.1021/acs.inorgchem.4c0536010.1021/acs.inorgchem.4c05360\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Reaction of [Ru(IPr)<sub>2</sub>(CO)H][BAr<sup>F</sup><sub>4</sub>] (<b>1</b>; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BAr<sup>F</sup><sub>4</sub> = B{3,5(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}<sub>4</sub>) with an excess of ZnH<sub>2</sub> in THF gives the structurally characterized neutral Ru(ZnH) complex [Ru(IPr)<sub>2</sub>(CO)(ZnH)H<sub>3</sub>] (<b>6</b>) and Ru(ZnH)<sub>2</sub> salt [Ru(IPr)<sub>2</sub>(CO)(ZnH)<sub>2</sub>H<sub>3</sub>][BAr<sup>F</sup><sub>4</sub>] (<b>5</b>). 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 <b>5</b>. At room temperature, this compound undergoes stoichiometric exchange with ZnMe<sub>2</sub> to give [Ru(IPr)<sub>2</sub>(CO)(ZnMe)<sub>2</sub>H<sub>3</sub>][BAr<sup>F</sup><sub>4</sub>] (<b>7</b>), and also proves to be catalytically active for the hydrogenation of 1-hexene and 5-hexene-2-one.</p><p >Zinc dihydride reacts with [Ru(IPr)<sub>2</sub>(CO)H][BAr<sup>F</sup><sub>4</sub>] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BAr<sup>F</sup><sub>4</sub> = B{C<sub>6</sub>H<sub>3</sub>(3,5-CF<sub>3</sub>)<sub>3</sub>}<sub>4</sub>) to afford the heterometallic ZnH-containing compounds [Ru(IPr)<sub>2</sub>(CO)(ZnH)<sub>2</sub>H<sub>3</sub>][BAr<sup>F</sup><sub>4</sub>] and [Ru(IPr)<sub>2</sub>(CO)(ZnH)H<sub>3</sub>]. Experiments and calculations have been used to probe the solution fluxionality and ZnH/ZnMe exchange of the former, which also proves to be catalytically active for alkene hydrogenation.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"64 8\",\"pages\":\"4043–4051 4043–4051\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-02-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acs.inorgchem.4c05360\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c05360\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c05360","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
ZnH2 as a Precursor to Catalytically Active Ru–ZnH Heterometallic Complexes
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.
Zinc dihydride reacts with [Ru(IPr)2(CO)H][BArF4] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BArF4 = B{C6H3(3,5-CF3)3}4) to afford the heterometallic ZnH-containing compounds [Ru(IPr)2(CO)(ZnH)2H3][BArF4] and [Ru(IPr)2(CO)(ZnH)H3]. Experiments and calculations have been used to probe the solution fluxionality and ZnH/ZnMe exchange of the former, which also proves to be catalytically active for alkene hydrogenation.
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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.
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