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,&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":"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":"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":"Isoelectronic Effects of Pt(II) Complexes with Nitrogen-Embedded Tetradentate Ligands on Blue Phosphorescence","authors":"Yuning Lin,&nbsp;Wenhuan Wang,&nbsp;Yueqi Wang,&nbsp;Yong Cao,&nbsp;Qinghua Xia*,&nbsp;Cong Zhang,&nbsp;Lei Ding and Xiao-Chun Hang*,&nbsp;","doi":"10.1021/acs.organomet.5c0009110.1021/acs.organomet.5c00091","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00091https://doi.org/10.1021/acs.organomet.5c00091","url":null,"abstract":"<p >Pt(II) complexes with tetradentate ligands have emerged as high-performance emitters in phosphorescent organic light-emitting diodes. Herein, a comprehensive study of <b>PtON1</b> [η⁴-(dimethylpyrazolyl)phenoxy-9-(pyridinyl-<i>N</i>-carbazole)Pt] analogues was done to learn the isoelectronic ligand effect on photo- and electroluminescent properties. By exchanging the phenyl ring in the <b>PtON1</b> framework for a pyridine ring, complexes of <b>PtON1-</b><i><b>o</b></i> and <b>PtON1-</b><i><b>p</b></i> exhibited better planarity in both ground and excited states and improved blue color with narrow emission spectra. A disproportionate energy variation was disclosed corresponding to the embedded nitrogen site. Compared with the initial prototype of <b>PtON1-dmp</b>, <b>PtON1-</b><i><b>o</b></i> exhibits enlargement in the lowest triplet excite-state energies (T₁), whereas <b>PtON1-</b><i><b>p</b></i> shows an opposite trend. The devices based on the nitrogen-embedded complex showed improved color purity in deep-blue emissions, in which <b>PtON1-</b><i><b>p</b></i> also exhibited the highest external quantum efficiency of 15.5% and the lowest turn-on voltage at 2.7 eV. This investigation envisioned an effective strategy to improve the emission properties via nitrogen-embedded isoelectronic derivatives.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1192–1199 1192–1199"},"PeriodicalIF":2.5,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238511","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 Insights into the Aerobic Oxidation of Methane to Formaldehyde over Cu–Zeolite","authors":"Ryoga Toyoshima,&nbsp;Ryoya Kugo,&nbsp;Yohei Kametani,&nbsp;Kazunari Yoshizawa,&nbsp;Sakae Takenaka and Yoshihito Shiota*,&nbsp;","doi":"10.1021/acs.organomet.5c0010810.1021/acs.organomet.5c00108","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00108https://doi.org/10.1021/acs.organomet.5c00108","url":null,"abstract":"<p >The catalytic cycle of methane (CH₄) oxidation mediated by Cu^II–OH species in the presence of molecular oxygen as an oxidant is discussed. The reaction pathways and energetics for the partial oxidation of CH₄ to formaldehyde on the AlO₄ surface of Cu–zeolite are computed and analyzed using the 3T cluster model at the B3LYP level of the theory. The presence of Cu^II–OH facilitates the C–H activation of CH₄. The activation energy for this process is calculated to be 27.0 kcal/mol. Subsequently, the oxygen in the system coordinates with the Cu atom, generating formaldehyde via the formation of Cu-oxyl species. The overall reaction for the partial oxidation of CH₄ is exothermic, with an energy change of 60.5 kcal/mol. Considering the activation energies of the catalytic cycle, the activation of the C–H bond of CH₄ and the cleavage of the O–O bond are comparable and are the rate-limiting processes for both. In addition, an alternative pathway begins with C–H bond cleavage by the copper-oxyl species, ultimately yielding formaldehyde. These findings suggest that Cu^II–OH can effectively induce C–H bond cleavage, which is crucial for informing design guidelines for zeolite catalysts. More interestingly, proton transfer, hydride transfer, and hydrogen-atom transfer are included in the catalytic cycle.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1124–1128 1124–1128"},"PeriodicalIF":2.5,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238588","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":"Tailoring of Pyridinium Amidate Palladium Complexes for Ethylene Conversion beyond Dimerization and for the Conversion of Higher α-Olefins","authors":"Esaïe Reusser,&nbsp;Barbara Milani and Martin Albrecht*,&nbsp;","doi":"10.1021/acs.organomet.5c0008710.1021/acs.organomet.5c00087","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00087https://doi.org/10.1021/acs.organomet.5c00087","url":null,"abstract":"<p >Ethylene polymerization with late transition metals offers the possibility of including polar monomers for the generation of functionalized polymers. However, several palladium complexes, including those with pyridyl-functionalized pyridinium amidate (PYA) ligands [Pd(Me)(MeCN)(N,N′)]⁺ (with N = PYA, N′ = pyridyl), undergo rapid β-hydrogen elimination and form predominantly butene derivatives. Here, we have modified a range of elements in the catalyst design, including (i) the PYA substituents (Me, Bu, CH₂OCH₃), (ii) the chelating imine donor, (iii) the labile neutral ligand L, and (iv) the noncoordinating anion. These variations indicated factors that prevent (L = lutidine) or slow down ethylene conversion (imine = oxalyl, triazolyl, and pyrazolyl) and factors that accelerate it. In particular, the absence of MeCN as the coordinating ligand and the introduction of BArF as the counterion are highly beneficial and lead to efficient ethylene conversion and formation of oligomers with C₂₀–C₃₀ chain length. Time-dependent reaction monitoring suggests a step-growth mechanism rather than the more common chain-growth mechanism with the initial formation of butene and the subsequent conversion of butene and higher olefins. Indeed, also higher α-olefins such as 1-hexene were oligomerized with this in situ-prepared catalytic PYA palladium system.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1176–1185 1176–1185"},"PeriodicalIF":2.5,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238501","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}