Ryan M. Tipker, Russell P. Hughes, David S. Glueck*, Heather A. Spinney, Michael A. Brammer and Arnold L. Rheingold,
{"title":"加氢甲酰化催化中 CO 从铑中置换出 P-Stereogenic Phosphiranes","authors":"Ryan M. Tipker, Russell P. Hughes, David S. Glueck*, Heather A. Spinney, Michael A. Brammer and Arnold L. Rheingold, ","doi":"10.1021/acs.organomet.3c00505","DOIUrl":null,"url":null,"abstract":"<p >The P-stereogenic phosphiranes <i>syn</i>- and <i>anti</i>-Mes*PCH<sub>2</sub>CHPh (<b>1</b>–<b>2</b>, Mes* = 2,4,6-(<i>t</i>-Bu)<sub>3</sub>C<sub>6</sub>H<sub>2</sub>) formed precatalysts for the hydroformylation of propylene using the precursor Rh(acac)(CO)<sub>2</sub>. Stoichiometric reactions gave the complexes Rh(acac)(L)(CO) (<b>3</b>–<b>4</b>). High-pressure NMR spectroscopy showed that Rh complex <b>3</b> was formed in the catalytic mixture, but on treatment with syngas (CO/H<sub>2</sub>), the phosphirane was displaced from rhodium. These observations were consistent with a density functional theory study, which found that the equilibrium between Rh(acac)(CO)<sub>2</sub>, phosphiranes <b>1</b>–<b>2</b>, CO, and Rh(acac)(L)(CO) (<b>3</b>–<b>4</b>) favored the starting materials. These results emphasized the competition between CO and phosphine ligands for coordination to rhodium during hydroformylation and the importance of strong Rh-L coordination to ensure control of catalyst properties.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 3","pages":"427–431"},"PeriodicalIF":2.9000,"publicationDate":"2024-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Displacement of P-Stereogenic Phosphiranes from Rhodium by CO in Hydroformylation Catalysis\",\"authors\":\"Ryan M. Tipker, Russell P. Hughes, David S. Glueck*, Heather A. Spinney, Michael A. Brammer and Arnold L. Rheingold, \",\"doi\":\"10.1021/acs.organomet.3c00505\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The P-stereogenic phosphiranes <i>syn</i>- and <i>anti</i>-Mes*PCH<sub>2</sub>CHPh (<b>1</b>–<b>2</b>, Mes* = 2,4,6-(<i>t</i>-Bu)<sub>3</sub>C<sub>6</sub>H<sub>2</sub>) formed precatalysts for the hydroformylation of propylene using the precursor Rh(acac)(CO)<sub>2</sub>. Stoichiometric reactions gave the complexes Rh(acac)(L)(CO) (<b>3</b>–<b>4</b>). High-pressure NMR spectroscopy showed that Rh complex <b>3</b> was formed in the catalytic mixture, but on treatment with syngas (CO/H<sub>2</sub>), the phosphirane was displaced from rhodium. These observations were consistent with a density functional theory study, which found that the equilibrium between Rh(acac)(CO)<sub>2</sub>, phosphiranes <b>1</b>–<b>2</b>, CO, and Rh(acac)(L)(CO) (<b>3</b>–<b>4</b>) favored the starting materials. These results emphasized the competition between CO and phosphine ligands for coordination to rhodium during hydroformylation and the importance of strong Rh-L coordination to ensure control of catalyst properties.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":\"43 3\",\"pages\":\"427–431\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-01-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.3c00505\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.3c00505","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Displacement of P-Stereogenic Phosphiranes from Rhodium by CO in Hydroformylation Catalysis
The P-stereogenic phosphiranes syn- and anti-Mes*PCH2CHPh (1–2, Mes* = 2,4,6-(t-Bu)3C6H2) formed precatalysts for the hydroformylation of propylene using the precursor Rh(acac)(CO)2. Stoichiometric reactions gave the complexes Rh(acac)(L)(CO) (3–4). High-pressure NMR spectroscopy showed that Rh complex 3 was formed in the catalytic mixture, but on treatment with syngas (CO/H2), the phosphirane was displaced from rhodium. These observations were consistent with a density functional theory study, which found that the equilibrium between Rh(acac)(CO)2, phosphiranes 1–2, CO, and Rh(acac)(L)(CO) (3–4) favored the starting materials. These results emphasized the competition between CO and phosphine ligands for coordination to rhodium during hydroformylation and the importance of strong Rh-L coordination to ensure control of catalyst properties.
期刊介绍：
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.
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