Organometallics最新文献

{"title":"Synthesis of Quinoline-Based Pt–Sb Complexes with L- or Z-Type Interaction: Ligand-Controlled Redox via Anion Transfer","authors":"Christopher K. Webber,&nbsp;Fanji Kong,&nbsp;Jugal Kumawat,&nbsp;Jyothish Joy,&nbsp;Erica K. Richardson,&nbsp;Paolo Siano,&nbsp;Diane A. Dickie,&nbsp;Daniel H. Ess* and T. Brent Gunnoe*,&nbsp;","doi":"10.1021/acs.organomet.4c0022110.1021/acs.organomet.4c00221","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00221https://doi.org/10.1021/acs.organomet.4c00221","url":null,"abstract":"<p >A series of Pt–Sb complexes with two or three L-type quinoline side arms were prepared and studied. Two ligands, tri(8-quinolinyl)stibane (SbQ₃, Q = 8-quinolinyl, <b>1</b>) and 8,8′-(phenylstibanediyl)diquinoline (SbQ₂Ph, <b>2</b>), were used to synthesize the Pt^II–Sb^III complexes (SbQ₃)PtCl₂ (<b>3</b>) and (SbQ₂Ph)PtCl₂ (<b>4</b>). Chloride abstraction with AgOAc provided the bis-acetate complexes (SbQ₃)Pt(OAc)₂ (<b>5</b>) and (SbQ₂Ph)Pt(OAc)₂ (<b>6</b>). To better understand the electronic effects of the Sb moiety, analogous bis-chloride complexes were oxidized to an overall formal oxidation state of +7 (i.e., Pt + Sb formal oxidation states = 7) using dichloro(phenyl)-λ³-iodane (PhICl₂) and 3,4,5,6-tetrachloro-1,2-dibenzoquinone (<i>o</i>-chloranil) as two-electron oxidants. Depending on the oxidant, different conformational changes occur within the coordination sphere of Pt as confirmed by single-crystal X-ray diffraction and NMR spectroscopy. In addition, the nature of Pt–Sb interactions was evaluated via molecular and localized orbital calculations.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00221","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142159399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pioneers and Influencers in Organometallic Chemistry: Alexander Nesmeyanov (1899–1980). Carbon and Hydrogen Are Good but What about the Other 100 Elements?","authors":"Elena K. Beloglazkina, Yuri A. Ustynyuk, Valentine G. Nenajdenko","doi":"10.1021/acs.organomet.4c00275","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00275","url":null,"abstract":"Alexander. N. Nesmeyanov (Figure 1) became one of the founders of a new scientific discipline─the chemistry of organoelement compounds. For many years, he was a recognized leader of the entire scientific community of the Soviet Union, heading Soviet science as President of the USSR Academy of Sciences (1951–1961). During the period of the Cold War, he managed not only to preserve but to strengthen and multiply ties of Russian scientists with the international community. Figure 1. Portrait of Alexander Nesmeyanov. As a student of N. Zelinsky, (1) who was the successor of V. Markovnikov at Moscow University, (2) he created one of the largest scientific schools in Russia. He was a man of many talents, possessing a rare combination of human qualities: a quick analytical mind and developed intuition, irreconcilability in upholding basic principles and the ability to find compromises, high demands on himself and on people, strictness in assessments, and soft benevolent humor. Combined with an extraordinary capacity for work, purposefulness, and organization, these qualities formed the basis of his outstanding achievements in science (Figure 2). Figure 2. Timeline of significant events in the life of Alexander Nesmeyanov─and in chemistry. Photos used are taken by the authors or adopted from public domains (https://ineos.ac.ru/history-directors/history-nesmeyanov; https://letopis.msu.ru/peoples/3157; https://ru.freepik.com/; https://ru.wikipedia.org). Alexander Nesmeyanov was born on September 9, 1899, in Moscow into a family of teachers. In 1917, he was admitted as a student of Moscow University, at the beginning of the Russian Revolution. The postrevolutionary years were difficult. Nesmeyanov worked as a night watchman at the faculty of chemistry and lived in a closet right in Zelinsky’s laboratory. By that time, the scientific interests of Zelinsky were more concentrated on catalytic hydrocarbon chemistry. Nesmeyanov wrote later: “Of course, this was very attractive and promising, but not for me. Carbon and hydrogen are good, but what about the other 100 elements?” (3) All his further life was inextricably linked with Moscow University: 1924, assistant professor; 1930, associate professor; 1934, doctor of sciences and full professor. From 1944 to 1978, he headed the Department of Organic Chemistry at the university. In addition, from 1943 to 1948 he was dean of the Faculty of Chemistry, and from 1948 to 1951 he was rector of Moscow University. Nesmeyanov’s first critical success came in 1929 after long, hard work and many failures. (4) He discovered a synthesis of organometallic compounds by thermal decomposition of double salts of aryldiazonium halides and heavy metal halides, now known as the “Nesmeyanov diazo method” (Scheme 1). Initially, this method was used to synthesize organomercury compounds. (5,6) Next, this reaction was successfully used for the synthesis of various organometallic compounds of tin, thallium, arsenic, antimony, and bismuth. ","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142180746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic Studies on Rh(III)-Catalyzed Defluorinative Annulation of N-Sulfonylarylamides with Ethyl 2-Diazo-3,3,3-Trifluoropropanoates","authors":"Zi-Ming Huang, Yi Sun, Yong Wang, Xing-Wang Wang","doi":"10.1021/acs.organomet.4c00249","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00249","url":null,"abstract":"The synthesis of fluorinated isoquinoline derivatives holds significant value in organic synthesis and medicine. Research into the reaction mechanisms and possible pathways for synthesizing these compounds plays a crucial role in advancing the development and applications of isoquinoline derivatives. Using density functional theory methods, we explored the reaction mechanism and potential pathways of the Rh(III)-catalyzed defluorinative annulation of N-sulfonylarylamides with ethyl 2-diazo-3,3,3-trifluoropropanoates. Theoretical calculations indicate that the reaction initiates with the formation of a metal carbene via C–H activation and denitrogenation, followed by migratory insertion. Subsequent steps involve metal-assisted β-fluoride elimination and anion exchange. Finally, intramolecular cyclization, defluorination, and sulfonyl migration yield isoquinoline products.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141948153","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pioneers and Influencers in Organometallic Chemistry: Alexander Nesmeyanov (1899–1980). Carbon and Hydrogen Are Good but What about the Other 100 Elements?","authors":"Elena K. Beloglazkina,&nbsp;Yuri A. Ustynyuk and Valentine G. Nenajdenko*,&nbsp;","doi":"10.1021/acs.organomet.4c0027510.1021/acs.organomet.4c00275","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00275https://doi.org/10.1021/acs.organomet.4c00275","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141972731","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic Studies on Rh(III)-Catalyzed Defluorinative Annulation of N-Sulfonylarylamides with Ethyl 2-Diazo-3,3,3-Trifluoropropanoates","authors":"Zi-Ming Huang,&nbsp;Yi Sun,&nbsp;Yong Wang* and Xing-Wang Wang*,&nbsp;","doi":"10.1021/acs.organomet.4c0024910.1021/acs.organomet.4c00249","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00249https://doi.org/10.1021/acs.organomet.4c00249","url":null,"abstract":"<p >The synthesis of fluorinated isoquinoline derivatives holds significant value in organic synthesis and medicine. Research into the reaction mechanisms and possible pathways for synthesizing these compounds plays a crucial role in advancing the development and applications of isoquinoline derivatives. Using density functional theory methods, we explored the reaction mechanism and potential pathways of the Rh(III)-catalyzed defluorinative annulation of N-sulfonylarylamides with ethyl 2-diazo-3,3,3-trifluoropropanoates. Theoretical calculations indicate that the reaction initiates with the formation of a metal carbene via C–H activation and denitrogenation, followed by migratory insertion. Subsequent steps involve metal-assisted β-fluoride elimination and anion exchange. Finally, intramolecular cyclization, defluorination, and sulfonyl migration yield isoquinoline products.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142159407","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrocatalytic Anaerobic Oxidation of Benzylic Amines Enabled by Ferrocene-Based Redox Mediators","authors":"Amy L. Waldbusser, Shabnam Hematian","doi":"10.1021/acs.organomet.4c00219","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00219","url":null,"abstract":"The generation and functionalization of carbon- or nitrogen-centered radicals are of great interest for their potential synthetic utility. Here, we report the anaerobic electrocatalytic oxidation of two primary benzylic amines, benzylamine and 2-picolylamine, in the presence of a catalytic quantity of an electron deficient ferrocene derivative as a single-electron redox mediator. The use of the appropriate redox mediator prevented fouling of the electrode surface and significantly decreased the potential at which the catalytic oxidation reaction occurred. Simulation of the electrochemical results revealed an E_rC_i′ catalytic process between the redox mediator and both substrates and significant difference in the electron transfer rate between the two substrates and electrochemically oxidized mediator. Through anaerobic controlled-potential electrolysis, we demonstrated a method with a Faradaic efficiency of 90% forming the desired coupled imine product of benzylamine oxidation while avoiding an excess of problematic overoxidation, hydrolysis, and other side reactions. Based on the electrochemical data along with the product analyses using IR and ¹H and ¹³C NMR spectroscopies, the proposed mechanistic steps for the redox mediated electrocatalytic process were laid out.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141948152","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Deactivation Modes in Nickel-Mediated Suzuki–Miyaura Cross-Coupling Reactions Using an NHC-Pyridonate Ligand","authors":"A. A. Kadam, Medina Afandiyeva, W. Brennessel, C. Kennedy","doi":"10.1021/acs.organomet.4c00235","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00235","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141921023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anisotropic π Bonding in Bis(iminoxolene)ruthenium: Consequences for Alkene and Alkyne Binding","authors":"Patricia Rose H. Ayson,&nbsp; and ,&nbsp;Seth N. Brown*,&nbsp;","doi":"10.1021/acs.organomet.4c0025910.1021/acs.organomet.4c00259","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00259https://doi.org/10.1021/acs.organomet.4c00259","url":null,"abstract":"<p >Orientational preferences in alkene and alkyne complexes arise from differences in the π backbonding capabilities of the relevant dπ orbitals, which typically are engendered by an unsymmetrical arrangement of ancillary ligands. The metal <i>trans</i>-bis(iminoxolene) fragment is <i>C</i>₂-symmetric but discriminates between perpendicular dπ orbitals because only one of them has a strong π interaction with the iminoxolenes. To assess this effect, square pyramidal bis(iminoxolene) alkene and alkyne complexes (Diso)₂Ru(L) (Diso = <i>N</i>-(2,6-diisopropylphenyl)-4,6-di-<i>tert</i>-butyl-<i>o</i>-iminobenzoquinone) are prepared via the bis-acetonitrile complex <i>cis</i>-(Diso)₂Ru(NCCH₃)₂. The alkenes and alkynes align roughly along the O–Ru–O axis but are turned slightly toward the cleft between the iminoxolene ligands, which orients the ligand π* orbital with the <i>d</i>π orbital that is not engaged in bonding with the iminoxolenes. In the alkyne complexes, π donation from the alkyne competes effectively with the ruthenium-iminoxolene π bonding, forming a favorable four-electron, three-orbital system. The barrier to rotation in the 1-hexyne complex is 19.0 kcal mol^–1, while allylbenzene dissociates more readily than it undergoes rotation, with a barrier of 17.4 kcal mol^–1. The strong orientational preference leads to high facial selectivity of alkene binding, with only one diastereomer of the 1-alkene adducts observed by NMR (&gt;30:1 selectivity).</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142159580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anisotropic π Bonding in Bis(iminoxolene)ruthenium: Consequences for Alkene and Alkyne Binding","authors":"P. Ayson, Seth N. Brown","doi":"10.1021/acs.organomet.4c00259","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00259","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141920998","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Iridium-Pentahydride Referee for Competition of Activations between C–H and C–F Bonds and between C–H Bonds Located in Different Positions","authors":"Ana Berges, Miguel A. Esteruelas, Ana M. López, Cristina Martín-Escura, E. Oñate","doi":"10.1021/acs.organomet.4c00251","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00251","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141922707","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}