Patricio Castillo, Bryan J Foley, Samuel R Lee, Billy J McCulloch, Nattamai Bhuvanesh, Oleg V Ozerov
{"title":"二芳胺/双（膦）PNP配体负载Os氢化物配合物的合成及（PNP）Ru和（PNP）Os配合物在C-H硼化催化中的应用","authors":"Patricio Castillo, Bryan J Foley, Samuel R Lee, Billy J McCulloch, Nattamai Bhuvanesh, Oleg V Ozerov","doi":"10.1021/acs.organomet.4c00388","DOIUrl":null,"url":null,"abstract":"<p><p>This manuscript describes the synthesis of Os complexes supported by the diarylamido/bis(phosphine) PNP pincer ligand. Compound (PNP)OsH(CO) (<b>3-Os</b>) was prepared by analogy with the previously reported <b>3-Ru</b>. However, attempts to make (PNP)OsH<sub>3</sub> (<b>4-Os</b>) analogously to <b>4-Ru</b> resulted in the formation of an unexpected compound (<b>5-Os</b>) that is a product of addition of a BH<sub>3</sub> unit across the Os-N bond in <b>4-Os</b>. Nonetheless, <b>4-Os</b> was prepared via an alternative route. Unlike <b>4-Ru</b>, <b>4-Os</b> appears to be a classical trihydride. Compounds <b>3-Ru</b>, <b>3-Os</b>, <b>4-Os</b>, <b>4-Ru</b>, and <b>5-Os</b> were tested as potential catalysts for (a) dehydrogenative borylation of terminal alkynes (DHBTA) and (b) dehydrogenative borylation of benzene. No catalytic C-H borylation was observed for any of them, but all of them catalyzed unselective hydroboration of 4-MeC<sub>6</sub>H<sub>4</sub>CCH.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 22","pages":"2944-2950"},"PeriodicalIF":2.5000,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11600505/pdf/","citationCount":"0","resultStr":"{\"title\":\"Synthesis of Os Hydride Complexes Supported by the Diarylamido/Bis(phosphine) PNP Ligand and Attempts at Using (PNP)Ru and (PNP)Os Complexes in C-H Borylation Catalysis.\",\"authors\":\"Patricio Castillo, Bryan J Foley, Samuel R Lee, Billy J McCulloch, Nattamai Bhuvanesh, Oleg V Ozerov\",\"doi\":\"10.1021/acs.organomet.4c00388\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>This manuscript describes the synthesis of Os complexes supported by the diarylamido/bis(phosphine) PNP pincer ligand. Compound (PNP)OsH(CO) (<b>3-Os</b>) was prepared by analogy with the previously reported <b>3-Ru</b>. However, attempts to make (PNP)OsH<sub>3</sub> (<b>4-Os</b>) analogously to <b>4-Ru</b> resulted in the formation of an unexpected compound (<b>5-Os</b>) that is a product of addition of a BH<sub>3</sub> unit across the Os-N bond in <b>4-Os</b>. Nonetheless, <b>4-Os</b> was prepared via an alternative route. Unlike <b>4-Ru</b>, <b>4-Os</b> appears to be a classical trihydride. Compounds <b>3-Ru</b>, <b>3-Os</b>, <b>4-Os</b>, <b>4-Ru</b>, and <b>5-Os</b> were tested as potential catalysts for (a) dehydrogenative borylation of terminal alkynes (DHBTA) and (b) dehydrogenative borylation of benzene. No catalytic C-H borylation was observed for any of them, but all of them catalyzed unselective hydroboration of 4-MeC<sub>6</sub>H<sub>4</sub>CCH.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":\"43 22\",\"pages\":\"2944-2950\"},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-11-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11600505/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.organomet.4c00388\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/11/25 0:00:00\",\"PubModel\":\"eCollection\",\"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.4c00388","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/11/25 0:00:00","PubModel":"eCollection","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Synthesis of Os Hydride Complexes Supported by the Diarylamido/Bis(phosphine) PNP Ligand and Attempts at Using (PNP)Ru and (PNP)Os Complexes in C-H Borylation Catalysis.
This manuscript describes the synthesis of Os complexes supported by the diarylamido/bis(phosphine) PNP pincer ligand. Compound (PNP)OsH(CO) (3-Os) was prepared by analogy with the previously reported 3-Ru. However, attempts to make (PNP)OsH3 (4-Os) analogously to 4-Ru resulted in the formation of an unexpected compound (5-Os) that is a product of addition of a BH3 unit across the Os-N bond in 4-Os. Nonetheless, 4-Os was prepared via an alternative route. Unlike 4-Ru, 4-Os appears to be a classical trihydride. Compounds 3-Ru, 3-Os, 4-Os, 4-Ru, and 5-Os were tested as potential catalysts for (a) dehydrogenative borylation of terminal alkynes (DHBTA) and (b) dehydrogenative borylation of benzene. No catalytic C-H borylation was observed for any of them, but all of them catalyzed unselective hydroboration of 4-MeC6H4CCH.
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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