Organometallics最新文献

{"title":"Triptycepenes: Synthesis, Metal Complexes, and Their Reactivity in Catalytic Reactions.","authors":"Shyam Sundar Mothuku, Uwe Monkowius, Marko Hapke","doi":"10.1021/acs.organomet.5c00102","DOIUrl":"10.1021/acs.organomet.5c00102","url":null,"abstract":"<p><p>An efficient protocol allows the convenient synthesis of substituted triptycepenes through the condensation of anthracene α-diketone with 3-pentanone or 1,3-diphenylpropan-2-one, finally yielding the corresponding cyclopentadienones. This approach offers a potential route toward sterically bulky cyclopentadienyl ligand frameworks. The methyl-substituted triptycepene was used to generate η⁵-coordinated Ru and Co complexes as well as an η⁴-coordinated Fe complex. These metal complexes were characterized by single-crystal X-ray diffraction, and their exemplary catalytic activity in metal-catalyzed reactions like cyclotrimerization, C-H functionalization, and transfer hydrogenation was investigated.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1200-1209"},"PeriodicalIF":2.5,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12152958/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144281727","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":"Triptycepenes: Synthesis, Metal Complexes, and Their Reactivity in Catalytic Reactions","authors":"Shyam Sundar Mothuku*,&nbsp;Uwe Monkowius and Marko Hapke*,&nbsp;","doi":"10.1021/acs.organomet.5c0010210.1021/acs.organomet.5c00102","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00102https://doi.org/10.1021/acs.organomet.5c00102","url":null,"abstract":"<p >An efficient protocol allows the convenient synthesis of substituted triptycepenes through the condensation of anthracene α-diketone with 3-pentanone or 1,3-diphenylpropan-2-one, finally yielding the corresponding cyclopentadienones. This approach offers a potential route toward sterically bulky cyclopentadienyl ligand frameworks. The methyl-substituted triptycepene was used to generate η⁵-coordinated Ru and Co complexes as well as an η⁴-coordinated Fe complex. These metal complexes were characterized by single-crystal X-ray diffraction, and their exemplary catalytic activity in metal-catalyzed reactions like cyclotrimerization, C–H functionalization, and transfer hydrogenation was investigated.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1200–1209 1200–1209"},"PeriodicalIF":2.5,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.5c00102","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144239165","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":"Corrections and Additions to “High-Valent Iridium Complexes Containing a Tripodal Bis-Cyclometalated C^N^C Ligand”","authors":"Rain Ng,&nbsp;Shun-Cheung Cheng,&nbsp;Ka-Lok Chan,&nbsp;Cheuk-Pui Leung,&nbsp;Wai-Man Cheung*,&nbsp;Herman H.-Y. Sung,&nbsp;Hung Kay Lee,&nbsp;Chi-Chiu Ko*,&nbsp;Ian D. Williams*,&nbsp;Zhenyang Lin* and Wa-Hung Leung*,&nbsp;","doi":"10.1021/acs.organomet.5c0018810.1021/acs.organomet.5c00188","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00188https://doi.org/10.1021/acs.organomet.5c00188","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1227 1227"},"PeriodicalIF":2.5,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144239140","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":"Synthesis, Characterization and Catalytic Activity of Iron, Cobalt and Nickel Complexes Bearing an N‑Heterocyclic Carbene-Based PCP Pincer Ligand.","authors":"Tiago F C Cruz, Daniel P Zobernig, Berthold Stöger, Ernst Pittenauer, Karl Kirchner","doi":"10.1021/acs.organomet.5c00172","DOIUrl":"10.1021/acs.organomet.5c00172","url":null,"abstract":"<p><p>Reactions of the bis-((R₂phosphanyl)-methyl)-1<i>H</i>-benzo-[<i>d</i>]-imidazole-3-ium hexafluorophosphate precursors [(PCP-R)-H]-PF₆ (R = <i>i</i>Pr, Ph) with zerovalent precursors [Fe₃(CO)₁₂], [Co₂(CO)₈], [Ni-(COD)₂] and [Ni-(PPh₃)₄], respectively, gave rise to the cationic iron, cobalt and nickel complexes [Fe-(PCP-<i>i</i>Pr)-(CO)₂H]-PF₆ (<b>1</b>), [Co-(PCP-<i>i</i>Pr)-(CO)₂]-PF₆ (<b>2</b>), [Co-(PCP-Ph)-(CO)₂]-PF₆ (<b>3</b>), [Ni-(PCP-<i>i</i>Pr)-(cyclooct-4-en-1-yl)]-PF₆ (<b>4</b>) and [Ni-(PCP-<i>i</i>Pr)-H]-PF₆ (<b>5</b>), by oxidative addition of the benzimidazolium CH bond in [(PCP-R)-H]-PF₆. The complexes bearing the bidentate ligand 3-((diisopropylphosphanyl)-methyl)-1-methyl-1H-benzo-[<i>d</i>]-imidazolidene PC-<i>i</i>Pr [Fe-(PC-<i>i</i>Pr)-(CO)₃] (<b>6</b>) and [Fe-(PC-<i>i</i>Pr)-(CO)₃H]-BF₄ (<b>7</b>) were also synthesized. All complexes were characterized by NMR and FTIR spectroscopies, high resolution mass spectrometry and selected cases by single-crystal X-ray diffraction. Cobalt complexes <b>2</b> and <b>3</b> were catalytically active in the hydroboration of styrene with pinacolborane (HBPin) using 1 mol % of precatalyst and 2 mol % of KO<i>t</i>Bu in THF at 70 °C for 18 h with yields of 87-93%. In addition, complex <b>2</b> also catalyzed the hydroboration of terminal alkenes in good yields (68-88%). Reaction of complex <b>2</b> with 5 equivs of HBPin and 2 equivs of KO<i>t</i>Bu in THF gave rise to the cobalt-(I) hydride complex [Co-(κ²-(P,C)-PCP-<i>i</i>Pr)-H-(CO)₂] (<b>8</b>), indicating that the mechanism of the catalytic process follows a cobalt-(I) hydride pathway.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1217-1226"},"PeriodicalIF":2.5,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12152947/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144281726","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":"Synthesis, Characterization and Catalytic Activity of Iron, Cobalt and Nickel Complexes Bearing an N-Heterocyclic Carbene-Based PCP Pincer Ligand","authors":"Tiago F. C. Cruz,&nbsp;Daniel P. Zobernig,&nbsp;Berthold Stöger,&nbsp;Ernst Pittenauer and Karl Kirchner*,&nbsp;","doi":"10.1021/acs.organomet.5c0017210.1021/acs.organomet.5c00172","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00172https://doi.org/10.1021/acs.organomet.5c00172","url":null,"abstract":"<p >Reactions of the bis((R₂phosphanyl)methyl)-1<i>H</i>-benzo[<i>d</i>]imidazole-3-ium hexafluorophosphate precursors [(PCP-R)H]PF₆ (R = <i>i</i>Pr, Ph) with zerovalent precursors [Fe₃(CO)₁₂], [Co₂(CO)₈], [Ni(COD)₂] and [Ni(PPh₃)₄], respectively, gave rise to the cationic iron, cobalt and nickel complexes [Fe(PCP-<i>i</i>Pr)(CO)₂H]PF₆ (<b>1</b>), [Co(PCP-<i>i</i>Pr)(CO)₂]PF₆ (<b>2</b>), [Co(PCP-Ph)(CO)₂]PF₆ (<b>3</b>), [Ni(PCP-<i>i</i>Pr)(cyclooct-4-en-1-yl)]PF₆ (<b>4</b>) and [Ni(PCP-<i>i</i>Pr)H]PF₆ (<b>5</b>), by oxidative addition of the benzimidazolium CH bond in [(PCP-R)H]PF₆. The complexes bearing the bidentate ligand 3-((diisopropylphosphanyl)methyl)-1-methyl-1H-benzo[<i>d</i>]imidazolidene PC-<i>i</i>Pr [Fe(PC-<i>i</i>Pr)(CO)₃] (<b>6</b>) and [Fe(PC-<i>i</i>Pr)(CO)₃H]BF₄ (<b>7</b>) were also synthesized. All complexes were characterized by NMR and FTIR spectroscopies, high resolution mass spectrometry and selected cases by single-crystal X-ray diffraction. Cobalt complexes <b>2</b> and <b>3</b> were catalytically active in the hydroboration of styrene with pinacolborane (HBPin) using 1 mol % of precatalyst and 2 mol % of KO<i>t</i>Bu in THF at 70 °C for 18 h with yields of 87–93%. In addition, complex <b>2</b> also catalyzed the hydroboration of terminal alkenes in good yields (68–88%). Reaction of complex <b>2</b> with 5 equivs of HBPin and 2 equivs of KO<i>t</i>Bu in THF gave rise to the cobalt(I) hydride complex [Co(κ²-(P,C)-PCP-<i>i</i>Pr)H(CO)₂] (<b>8</b>), indicating that the mechanism of the catalytic process follows a cobalt(I) hydride pathway.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1217–1226 1217–1226"},"PeriodicalIF":2.5,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.5c00172","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144239139","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":"Flash Communication: N-Heterocyclic Carbene Nickel-Mediated C–C Activation of Substituted Vinylcyclobutanes","authors":"Cherish Nie,&nbsp;Marina Pérez-Jiménez,&nbsp;Junho Kim and Paul J. Chirik*,&nbsp;","doi":"10.1021/acs.organomet.5c0013010.1021/acs.organomet.5c00130","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00130https://doi.org/10.1021/acs.organomet.5c00130","url":null,"abstract":"<p >The C–C activation of three substituted vinylcyclobutanes by [(IPr)Ni(0)] (IPr = ((1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) complexes was evaluated. Both 1,2-dicyclobutylethylene and β-caryophyllene underwent oxidative ring-opening with [(IPr)Ni(0)] to furnish isolable 7-membered alkyl, allyl-metallacycles at ambient temperature. In contrast, a derivative of β-caryophyllene bearing terminal alkenes resulted in formation of an isolable nickel bis(olefin) complex that exhibited only partial conversion to the metallacycle upon heating to 80 °C.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1134–1137 1134–1137"},"PeriodicalIF":2.5,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238383","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":"Synthesis of Diamido N-Heterocyclic Imines (DAC = NH) Via Staudinger or Reductive N–N Bond Cleavage Approach","authors":"Kajal Balayan,&nbsp;Himanshu Sharma,&nbsp;Kumar Vanka,&nbsp;Rajesh G. Gonnade and Sakya S. Sen*,&nbsp;","doi":"10.1021/acs.organomet.5c0012010.1021/acs.organomet.5c00120","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00120https://doi.org/10.1021/acs.organomet.5c00120","url":null,"abstract":"<p >This report communicates the first examples of N-heterocyclic imines based on electrophilic diamido carbenes (DACs). While <b>2</b> is prepared by classical Staudinger synthesis, <b>4</b> is obtained via an unusual reductive N–N bond cleavage of an azine by HCl. The exocyclic C═N bond lengths in <b>2</b> and <b>4</b> are substantially shorter than those based on N-heterocyclic carbenes and cyclic (alkyl)(amino)carbene reflecting the electrophilic character of DACs.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1129–1133 1129–1133"},"PeriodicalIF":2.5,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238619","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":"","authors":"J. Pablo Martínez*,&nbsp;Dariusz Lewandowski,&nbsp;Grzegorz Hreczycho* and Bartosz Trzaskowski*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 10","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.5,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00090","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144448208","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":"","authors":"Errikos Kounalis,&nbsp;Marieke M. Broekman,&nbsp;Puck Uyttewaal,&nbsp;Uladzislava Dabranskaya,&nbsp;Martin Lutz and Daniël L. J. Broere*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 10","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.5,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00070","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144362196","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":"","authors":"Tatyana V. Balashova*,&nbsp;Svetlana K. Polyakova,&nbsp;Vasily A. Ilichev,&nbsp;Ivan D. Grishin,&nbsp;Roman V. Rumyantcev,&nbsp;Georgy K. Fukin,&nbsp;Alexey V. Marugin and Mikhail N. Bochkarev*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 10","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.5,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00071","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144362197","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}