Vanessa R. G. Cacho, Luís F. Veiros, Clara S. B. Gomes, Mariana Sardo, Cláudia A. Figueira, Ana M. Martins, Maria João Ferreira
{"title":"P,N 配体支持的钌配合物中通过氢化作用裂解 C-P 键","authors":"Vanessa R. G. Cacho, Luís F. Veiros, Clara S. B. Gomes, Mariana Sardo, Cláudia A. Figueira, Ana M. Martins, Maria João Ferreira","doi":"10.1021/acs.inorgchem.4c04275","DOIUrl":null,"url":null,"abstract":"The reactivity of ruthenium hydride complexes supported by 2-((di-<i>tert</i>-butylphosphaneyl)methyl)pyridine, <b>L1</b> and 2-(di-<i>tert</i>-butylphosphaneyl)pyridine, <b>L2</b>, was explored. The reaction of {Ru(COD)Cl<sub>2</sub>}<sub><i>x</i></sub> with <b>L1</b> in the presence of base and 10 bar of H<sub>2</sub> gave the expected complex [Ru(L1)<sub>2</sub>(H)Cl], <b>1</b>, while the same reaction with <b>L2</b> gave [Ru(L2)(P(H)<sup><i>t</i></sup>Bu<sub>2</sub>)(H)Cl], <b>2</b>, that results from the cleavage of a C–P bond. We were able to establish that under the reaction conditions the first species formed is [Ru(L2)<sub>2</sub>(H)Cl], <b>3</b>, and that this species decomposes to give complex <b>2</b> and is in equilibrium with [Ru(L<sub>2</sub>)<sub>2</sub>Cl<sub>2</sub>], <b>4</b>. The proposed mechanism obtained by DFT has the protonation of the carbon as the highest energy step (38.9 kcal/mol), consistent with a slow reaction. Preliminary studies reveal that complex <b>2</b> is a very active catalyst in the hydrogenation of benzaldehyde (TONs up to 44,000).","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"44 1","pages":""},"PeriodicalIF":4.3000,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"C–P Bond Cleavage Through Hydrogenation in Ruthenium Complexes Supported by P,N Ligands\",\"authors\":\"Vanessa R. G. Cacho, Luís F. Veiros, Clara S. B. Gomes, Mariana Sardo, Cláudia A. Figueira, Ana M. Martins, Maria João Ferreira\",\"doi\":\"10.1021/acs.inorgchem.4c04275\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The reactivity of ruthenium hydride complexes supported by 2-((di-<i>tert</i>-butylphosphaneyl)methyl)pyridine, <b>L1</b> and 2-(di-<i>tert</i>-butylphosphaneyl)pyridine, <b>L2</b>, was explored. The reaction of {Ru(COD)Cl<sub>2</sub>}<sub><i>x</i></sub> with <b>L1</b> in the presence of base and 10 bar of H<sub>2</sub> gave the expected complex [Ru(L1)<sub>2</sub>(H)Cl], <b>1</b>, while the same reaction with <b>L2</b> gave [Ru(L2)(P(H)<sup><i>t</i></sup>Bu<sub>2</sub>)(H)Cl], <b>2</b>, that results from the cleavage of a C–P bond. We were able to establish that under the reaction conditions the first species formed is [Ru(L2)<sub>2</sub>(H)Cl], <b>3</b>, and that this species decomposes to give complex <b>2</b> and is in equilibrium with [Ru(L<sub>2</sub>)<sub>2</sub>Cl<sub>2</sub>], <b>4</b>. The proposed mechanism obtained by DFT has the protonation of the carbon as the highest energy step (38.9 kcal/mol), consistent with a slow reaction. Preliminary studies reveal that complex <b>2</b> is a very active catalyst in the hydrogenation of benzaldehyde (TONs up to 44,000).\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"44 1\",\"pages\":\"\"},\"PeriodicalIF\":4.3000,\"publicationDate\":\"2024-11-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.inorgchem.4c04275\",\"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://doi.org/10.1021/acs.inorgchem.4c04275","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
C–P Bond Cleavage Through Hydrogenation in Ruthenium Complexes Supported by P,N Ligands
The reactivity of ruthenium hydride complexes supported by 2-((di-tert-butylphosphaneyl)methyl)pyridine, L1 and 2-(di-tert-butylphosphaneyl)pyridine, L2, was explored. The reaction of {Ru(COD)Cl2}x with L1 in the presence of base and 10 bar of H2 gave the expected complex [Ru(L1)2(H)Cl], 1, while the same reaction with L2 gave [Ru(L2)(P(H)tBu2)(H)Cl], 2, that results from the cleavage of a C–P bond. We were able to establish that under the reaction conditions the first species formed is [Ru(L2)2(H)Cl], 3, and that this species decomposes to give complex 2 and is in equilibrium with [Ru(L2)2Cl2], 4. The proposed mechanism obtained by DFT has the protonation of the carbon as the highest energy step (38.9 kcal/mol), consistent with a slow reaction. Preliminary studies reveal that complex 2 is a very active catalyst in the hydrogenation of benzaldehyde (TONs up to 44,000).
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.
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