{"title":"由吡啶稳定磷酰化物衍生的第 9 和第 10 组 C 供体配体","authors":"Anushree Poddar, F. Christopher Pigge","doi":"10.1021/acs.organomet.4c00204","DOIUrl":null,"url":null,"abstract":"The design and synthesis of η<sup>1</sup>-C-donor ligands that combine nucleophilic 4-alkylidene dihydropyridines with phosphorus ylides is reported. Positioning of a phosphonium group at the picolyl carbon of 4-alkylpyridinium salts allows for conversion to phosphonium-stabilized alkylidene dihydropyridine ligands under mildly basic conditions. The resulting (Me-N-Py-CH-PPh<sub>2</sub>-R)(BF<sub>4</sub>) ligands coordinate Pd(II)Cl<sub>2</sub> as monodentate (R = Ph) or bidentate ligands (R = 2-Py, CH<sub>2</sub>PPh<sub>2</sub>, or CH<sub>2</sub>CH<sub>2</sub>PPh<sub>2</sub>), and six new Pd(II) complexes were spectroscopically characterized. Structural features of four of the complexes were further defined through single-crystal X-ray diffractometry. The ligands in these complexes are best described as phosphorus ylide C-donors that are stabilized by adjacent <i>N</i>-methylpyridinium rings. In addition, two Rh(I) complexes were successfully prepared and characterized, including a Rh(I) carbonyl complex which exhibited a low ν<sub>CO</sub> of 1984 cm<sup>–1</sup>, indicative of the strong σ-donor properties of these ligands. The ability of a Pd complex to catalyze Suzuki cross-coupling reactions was examined.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Groups 9 and 10 Complexes of C–Donor Ligands Derived from Pyridinium-Stabilized Phosphorus Ylides\",\"authors\":\"Anushree Poddar, F. Christopher Pigge\",\"doi\":\"10.1021/acs.organomet.4c00204\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The design and synthesis of η<sup>1</sup>-C-donor ligands that combine nucleophilic 4-alkylidene dihydropyridines with phosphorus ylides is reported. Positioning of a phosphonium group at the picolyl carbon of 4-alkylpyridinium salts allows for conversion to phosphonium-stabilized alkylidene dihydropyridine ligands under mildly basic conditions. The resulting (Me-N-Py-CH-PPh<sub>2</sub>-R)(BF<sub>4</sub>) ligands coordinate Pd(II)Cl<sub>2</sub> as monodentate (R = Ph) or bidentate ligands (R = 2-Py, CH<sub>2</sub>PPh<sub>2</sub>, or CH<sub>2</sub>CH<sub>2</sub>PPh<sub>2</sub>), and six new Pd(II) complexes were spectroscopically characterized. Structural features of four of the complexes were further defined through single-crystal X-ray diffractometry. The ligands in these complexes are best described as phosphorus ylide C-donors that are stabilized by adjacent <i>N</i>-methylpyridinium rings. In addition, two Rh(I) complexes were successfully prepared and characterized, including a Rh(I) carbonyl complex which exhibited a low ν<sub>CO</sub> of 1984 cm<sup>–1</sup>, indicative of the strong σ-donor properties of these ligands. The ability of a Pd complex to catalyze Suzuki cross-coupling reactions was examined.\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-07-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.organomet.4c00204\",\"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://doi.org/10.1021/acs.organomet.4c00204","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Groups 9 and 10 Complexes of C–Donor Ligands Derived from Pyridinium-Stabilized Phosphorus Ylides
The design and synthesis of η1-C-donor ligands that combine nucleophilic 4-alkylidene dihydropyridines with phosphorus ylides is reported. Positioning of a phosphonium group at the picolyl carbon of 4-alkylpyridinium salts allows for conversion to phosphonium-stabilized alkylidene dihydropyridine ligands under mildly basic conditions. The resulting (Me-N-Py-CH-PPh2-R)(BF4) ligands coordinate Pd(II)Cl2 as monodentate (R = Ph) or bidentate ligands (R = 2-Py, CH2PPh2, or CH2CH2PPh2), and six new Pd(II) complexes were spectroscopically characterized. Structural features of four of the complexes were further defined through single-crystal X-ray diffractometry. The ligands in these complexes are best described as phosphorus ylide C-donors that are stabilized by adjacent N-methylpyridinium rings. In addition, two Rh(I) complexes were successfully prepared and characterized, including a Rh(I) carbonyl complex which exhibited a low νCO of 1984 cm–1, indicative of the strong σ-donor properties of these ligands. The ability of a Pd complex to catalyze Suzuki cross-coupling reactions was examined.
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.