{"title":"含nhc基pcp型钳形配体的氮化钼配合物对不饱和底物的反应性","authors":"Tomoyuki Miyazaki, Shun Suginome, Taiji Nakamura, Hiromasa Tanaka, Kazunari Yoshizawa, Yoshiaki Nishibayashi","doi":"10.1039/d5dt02036k","DOIUrl":null,"url":null,"abstract":"Reactivity of a molybdenum–nitride complex bearing an N-heterocyclic carbene (NHC)-based PCP-type pincer ligand (1), whose nitride ligand is derived from dinitrogen, toward various unsaturated substrates was systematically investigated. The reaction of complex 1 with carbon monoxide as a substrate featuring a C–O triple bond afforded the corresponding cationic nitride–carbonyl complex, where the carbonyl ligand is coordinated to the molybdenum centre in place of the iodine ligand. Reactions of complex 1 with 1-pentyne, ethylene, and maleic anhydride as substrates featuring a C–C multiple bond afforded the corresponding π-complexes, where the C–C multiple bond is coordinated to the molybdenum centre. The reaction of 1 with dioxygen also yielded the corresponding π-complex in a similar manner to the reaction with ethylene. Finally, we investigated the redox reactivities of nitride–carbonyl and nitride–alkyne complexes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"23 1","pages":""},"PeriodicalIF":3.3000,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Reactivity of molybdenum–nitride complex bearing NHC-based PCP-type pincer ligand toward unsaturated substrates\",\"authors\":\"Tomoyuki Miyazaki, Shun Suginome, Taiji Nakamura, Hiromasa Tanaka, Kazunari Yoshizawa, Yoshiaki Nishibayashi\",\"doi\":\"10.1039/d5dt02036k\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Reactivity of a molybdenum–nitride complex bearing an N-heterocyclic carbene (NHC)-based PCP-type pincer ligand (1), whose nitride ligand is derived from dinitrogen, toward various unsaturated substrates was systematically investigated. The reaction of complex 1 with carbon monoxide as a substrate featuring a C–O triple bond afforded the corresponding cationic nitride–carbonyl complex, where the carbonyl ligand is coordinated to the molybdenum centre in place of the iodine ligand. Reactions of complex 1 with 1-pentyne, ethylene, and maleic anhydride as substrates featuring a C–C multiple bond afforded the corresponding π-complexes, where the C–C multiple bond is coordinated to the molybdenum centre. The reaction of 1 with dioxygen also yielded the corresponding π-complex in a similar manner to the reaction with ethylene. Finally, we investigated the redox reactivities of nitride–carbonyl and nitride–alkyne complexes.\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\"23 1\",\"pages\":\"\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2025-09-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d5dt02036k\",\"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":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5dt02036k","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Reactivity of a molybdenum–nitride complex bearing an N-heterocyclic carbene (NHC)-based PCP-type pincer ligand (1), whose nitride ligand is derived from dinitrogen, toward various unsaturated substrates was systematically investigated. The reaction of complex 1 with carbon monoxide as a substrate featuring a C–O triple bond afforded the corresponding cationic nitride–carbonyl complex, where the carbonyl ligand is coordinated to the molybdenum centre in place of the iodine ligand. Reactions of complex 1 with 1-pentyne, ethylene, and maleic anhydride as substrates featuring a C–C multiple bond afforded the corresponding π-complexes, where the C–C multiple bond is coordinated to the molybdenum centre. The reaction of 1 with dioxygen also yielded the corresponding π-complex in a similar manner to the reaction with ethylene. Finally, we investigated the redox reactivities of nitride–carbonyl and nitride–alkyne complexes.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.