Organometallics最新文献_第9页

Crystal-Field Properties of Pentalene Ligands in Erbium(III) Sandwich Complexes 铒（III）夹层配合物中戊二烯配体的晶体场性质。

IF 2.4 3区化学

Organometallics Pub Date : 2026-07-27 Epub Date: 2026-07-07 DOI: 10.1021/acs.organomet.6c00171

Siddhartha De, Arpan Mondal, F. Geoffrey N. Cloke, Jinkui Tang, Richard A. Layfield

{"title":"Crystal-Field Properties of Pentalene Ligands in Erbium(III) Sandwich Complexes","authors":"Siddhartha De, Arpan Mondal, F. Geoffrey N. Cloke, Jinkui Tang, Richard A. Layfield","doi":"10.1021/acs.organomet.6c00171","DOIUrl":"10.1021/acs.organomet.6c00171","url":null,"abstract":"The influence of pentalene ligands on the crystal-fieldpropertiesof erbium(III) has been examined using the monometallic complexes[Er(η8-Pn†)2]− (1) and [(η8-Pn†)Er(η8-COT)]− (2)(Pn† = [1,4-(iPr3Si)2C8H4]2–, COT = [C8H8]2–), whichwere synthesized as [K(2.2.2-crypt)]+ salts. Both compoundsdisplay magnetic anisotropy consistent with the prolate ion Er3+, but do not exhibit slow magnetic relaxation in zero field.Field-induced AC susceptibility measurements show that relaxationis governed by Raman and quantum tunnelling processes, with no evidencefor an Orbach mechanism. Multireference ab initio calculations revealanisotropic ground Kramers doublets with significant transverse componentsin both 1 and 2, along with extensive MJ mixing and low-lying excitedstates that enable efficient relaxation. Structural analysis showsthat the pentalene ligands enforce a low-symmetry coordination environment,which is only partially moderated by incorporation of a cyclo-octatetraenylligand in 2. These results indicate that the pentaleneligands impose a local symmetry on erbium(III) that facilitates transverseanisotropy and effectively precludes single-molecule magnet behavior.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 14","pages":"1740–1745"},"PeriodicalIF":2.4,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148617496","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}

引用次数: 0

Flash Communication: Double Migratory Insertion in Digold(I) Acetylides 闪光通讯：双金(I)乙酰基醚的双迁移插入

IF 2.4 3区化学

Organometallics Pub Date : 2026-07-27 Epub Date: 2026-05-29 DOI: 10.1021/acs.organomet.6c00123

Juan Cayuela-Castillo, Ignacio Nieto-Vargas, Francisco J. Fernández-de-Córdova, Pablo Ríos

引用次数: 0

NMR and DFT Characterization of Pd Complexes Observed during Pd-Catalyzed Arylation of Hydrodisilanes 钯催化氢二烷芳基化过程中钯配合物的NMR和DFT表征

IF 2.4 3区化学

Organometallics Pub Date : 2026-07-27 Epub Date: 2026-07-16 DOI: 10.1021/acs.organomet.6c00006

Kei-ichi Sato, Kazuhiko Yamasaki, Mineyuki Hattori, Masaki Nishio, Kenichiro Omoto, Daisuke Yokogawa, Showa Kitajima, Hitoshi Kasai, Kouki Oka, Yoshinori Yamanoi

引用次数: 0

1,2,3-Triazole-Bridged Binuclear Iridium Pincer Complexes: Comparing Reactivities with Monometallic Analogues 1,2,3-三唑桥接双核铱钳形配合物：与单金属类似物的反应性比较

IF 2.4 3区化学

Organometallics Pub Date : 2026-07-27 Epub Date: 2026-07-14 DOI: 10.1021/acs.organomet.6c00133

Jesvita Cardozo, Ouchan He, Mike Ahrens, Emilia Velasquez Böhm, Thomas Braun

{"title":"1,2,3-Triazole-Bridged Binuclear Iridium Pincer Complexes: Comparing Reactivities with Monometallic Analogues","authors":"Jesvita Cardozo, Ouchan He, Mike Ahrens, Emilia Velasquez Böhm, Thomas Braun","doi":"10.1021/acs.organomet.6c00133","DOIUrl":"10.1021/acs.organomet.6c00133","url":null,"abstract":"Binuclear iridium–pincer complexes bearing metalcenterswith different coordination spheres could provide a promising platformfor new reactivities and enable cooperative catalytic properties.Herein, we report the synthesis of the Ir(III)–Ir(III) pincercomplexes [(tBuPOCN3N2COtBuP)Ir2(H)2(acac)2] (3b) and [CF3–(tBuPOCN3N2COtBuP)Ir2(H)2(μ-OAc)(μ-Cl)](4b). For each complex, a bridging 1,2,3-triazole scaffoldin the ligand framework allows for two distinctive Ir–POCNpincer moieties, one having an Ir–N3 bond and theother fragment with a hemilabile Ir–N2 coordination.Comparative studies on the structures, reactivity, and catalytic transferdehydrogenation activity of these complexes with the reactivity oftheir monomeric analogues─the previously reported [(tBuPOCN3Triaz)Ir(H)(acac)] (1b) and independently synthesized [(tBuPOCN2Triaz)Ir(H)(acac)] (2b)─are further described. While subsequent reactivity of themononuclear complexes with CO affords the Ir(I) monocarbonyl complexes,the binuclear complexes instead result in mixed valent Ir(I)–Ir(III)tricarbonyl species. The described binuclear complexes and their reactivityproducts are the original examples of systems containing nonidenticaliridium pincers within the same framework.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 14","pages":"1712–1721"},"PeriodicalIF":2.4,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148656408","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}

引用次数: 0

Benchmarking the Electron Donor Strength of Phenyl Tris(2-pyridyl)borate (Tpy–) with TpyMn(CO)3 and by Bordwell pKa Analysis 用TpyMn(CO)3和Bordwell pKa分析对苯基三（2-吡啶基）硼酸酯（Tpy -）的电子供体强度进行基准测试

IF 2.4 3区化学

Organometallics Pub Date : 2026-07-27 Epub Date: 2026-07-10 DOI: 10.1021/acs.organomet.6c00191

Oshani Wijesinghe, Adam Czader, Robert J. Comito

{"title":"Benchmarking the Electron Donor Strength of Phenyl Tris(2-pyridyl)borate (Tpy–) with TpyMn(CO)3 and by Bordwell pKa Analysis","authors":"Oshani Wijesinghe, Adam Czader, Robert J. Comito","doi":"10.1021/acs.organomet.6c00191","DOIUrl":"10.1021/acs.organomet.6c00191","url":null,"abstract":"Tris(2-pyridyl)borate ligands are an emerging class ofrobust andelectron-rich scorpionate ligands. We investigated the relative electrondonor strength of phenyl tris(2-pyridyl)borate (Tpy–) by the synthesis of reporter compound TpyMn(CO)3 and by pKa analysis. Comparisonof the A1-symmetric carbonyl stretching wavenumber (2020cm–1) for TpyMn(CO)3 to those for analogousLMn(CO)3 complexes suggests that Tpy– is a comparable electron donor to Cp*– (pentamethylcyclopentadienide),a stronger donor than tris(pyrazolyl)borates or Cp– (cyclopentadienide), and a weaker donor than tris(phosphinomethyl)borate, tris(mercaptoimidazolyl)borate,and tris(imidazoline)borate ligands. We also obtainedpKas in DMSO by Bordwell’s methodfor TpyH (16.3) and for TpyH2+ (8.5), representativeprecursors for Tpy– complex synthesis. Tpy– is actually less basic than Cp– (the pKa of CpH is 18.0), underlying the facile synthesisof electron-rich complexes by mild proton exchange from TpyH.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 14","pages":"1639–1643"},"PeriodicalIF":2.4,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148656413","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}

引用次数: 0

Calcium Alkynyl(hydrido)zincates 炔基钙锌酸盐(hydrido)。

IF 2.4 3区化学

Organometallics Pub Date : 2026-07-27 Epub Date: 2026-07-09 DOI: 10.1021/acs.organomet.6c00164

Marcos López-Aguilar, Kyle G. Pearce, Michael S. Hill

{"title":"Calcium Alkynyl(hydrido)zincates","authors":"Marcos López-Aguilar, Kyle G. Pearce, Michael S. Hill","doi":"10.1021/acs.organomet.6c00164","DOIUrl":"10.1021/acs.organomet.6c00164","url":null,"abstract":"The β-diketiminato calcium hydride dimer, [(BDI)CaH]2 (BDI = HC{(Me)CNDipp}2; Dipp = 2,6-i-Pr2C6H3), reacts with [ZnTMP2] in the presence of terminal alkynes to provide a structurallydiverse series of heterobimetallic calcium–zinc acetylide derivatives.Reactions employing two equivalents of alkyne yield the dialkynyl(hydrido)zincates,[(BDI)Ca(μ-C≡CR)(μ-TMP)Zn(μ-H)]2 (R = nBu, Ph), which undergo ligandredistribution to afford the corresponding β-diketiminato calciumacetylides. Conversely, use of four equivalents of alkyne resultsin further substitution at zinc to provide the tetrakis(alkynyl)zincates,[(BDI)Ca(μ-C≡CnBu)2Zn(μ-H)]2 and [(BDI)Ca(μ-C≡CPh)2Zn(μ-C≡CPh)2Ca(BDI)]. In contrast,an attempt to synthesize a similarly higher order calcium zincatebut containing differentiated alkynyl substituents, by reaction of[(BDI)Ca(μ-C≡CnBu)(μ-TMP)Zn(μ-H)]2 and PhC≡CH, provided [(THF)2Ca(μ-C≡CPh)3Zn(CH2Ph)]2, resulting from tolueneactivation and after addition of THF as the only identifiable product.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 14","pages":"1722–1730"},"PeriodicalIF":2.4,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148617524","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}

引用次数: 0

1,2,3-Triazole-Bridged Binuclear Iridium Pincer Complexes: Comparing Reactivities with Monometallic Analogues 1,2,3-三唑桥接双核铱钳形配合物：与单金属类似物的反应性比较

IF 2.4 3区化学

Organometallics Pub Date : 2026-07-27 Epub Date: 2026-07-14 DOI: 10.1021/acs.organomet.6c00133

Jesvita Cardozo, Ouchan He, Mike Ahrens, Emilia Velasquez Böhm, Thomas Braun

{"title":"1,2,3-Triazole-Bridged Binuclear Iridium Pincer Complexes: Comparing Reactivities with Monometallic Analogues","authors":"Jesvita Cardozo, Ouchan He, Mike Ahrens, Emilia Velasquez Böhm, Thomas Braun","doi":"10.1021/acs.organomet.6c00133","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00133","url":null,"abstract":"Binuclear iridium–pincer complexes bearing metalcenterswith different coordination spheres could provide a promising platformfor new reactivities and enable cooperative catalytic properties.Herein, we report the synthesis of the Ir(III)–Ir(III) pincercomplexes [(tBuPOCN3N2COtBuP)Ir2(H)2(acac)2] (3b) and [CF3–(tBuPOCN3N2COtBuP)Ir2(H)2(μ-OAc)(μ-Cl)](4b). For each complex, a bridging 1,2,3-triazole scaffoldin the ligand framework allows for two distinctive Ir–POCNpincer moieties, one having an Ir–N3 bond and theother fragment with a hemilabile Ir–N2 coordination.Comparative studies on the structures, reactivity, and catalytic transferdehydrogenation activity of these complexes with the reactivity oftheir monomeric analogues─the previously reported [(tBuPOCN3Triaz)Ir(H)(acac)] (1b) and independently synthesized [(tBuPOCN2Triaz)Ir(H)(acac)] (2b)─are further described. While subsequent reactivity of themononuclear complexes with CO affords the Ir(I) monocarbonyl complexes,the binuclear complexes instead result in mixed valent Ir(I)–Ir(III)tricarbonyl species. The described binuclear complexes and their reactivityproducts are the original examples of systems containing nonidenticaliridium pincers within the same framework.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 14","pages":"1712–1721"},"PeriodicalIF":2.4,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148656312","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}

引用次数: 0

Hydroaminoalkylation and Zinc Cross-linking: A Pathway to Recyclable Polybutadiene Materials 氢胺烷基化和锌交联：可回收聚丁二烯材料的途径

IF 2.4 3区化学

Organometallics Pub Date : 2026-07-27 Epub Date: 2026-07-11 DOI: 10.1021/acs.organomet.6c00099

Saeed Ataie, Amir Malmir, Keegan Milliken, Hala Belghitri, Quentin Chan, Savvas G. Hatzikiriakos, Laurel L. Schafer

{"title":"Hydroaminoalkylation and Zinc Cross-linking: A Pathway to Recyclable Polybutadiene Materials","authors":"Saeed Ataie, Amir Malmir, Keegan Milliken, Hala Belghitri, Quentin Chan, Savvas G. Hatzikiriakos, Laurel L. Schafer","doi":"10.1021/acs.organomet.6c00099","DOIUrl":"10.1021/acs.organomet.6c00099","url":null,"abstract":"The catalytic hydroaminoalkylationof 1,2-polybutadiene(PBD) inpostpolymerization modification has been employed to introduce aminefunctionalities into PBD50, a commercial polybutadiene containing∼70 wt % 1,2-vinyl units. This amine introduction significantlyenhances the bulk properties of PBD, including increased glass transitiontemperature, improved viscoelastic behavior, and greater resistanceto flow. In this study, we present a novel approach for cross-linkingaminated PBD, where the pendant amine groups coordinate to zinc centers,forming N–Zn bonds that link the polymer chains. This chainextension strategy yields materials with higher glass transition temperatures,increased zero-shear viscosity, and more solid-like viscoelastic behavior,reaching values comparable to those obtained with significantly higheramine loadings. Notably, the cross-linked PBD materials exhibit exceptionalrecyclability, as simple acid treatment effectively removes the cross-linking,restoring the original aminated PBD. This work demonstrates a sustainableand efficient proof-of-concept strategy for developing recyclablePBD-based materials, highlighting the potential of zinc-mediated chainextension as a general approach for designing dynamic and reprocessablepolymers.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 14","pages":"1691–1697"},"PeriodicalIF":2.4,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148624779","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}

引用次数: 0

Cobalt Boryl Complexes: Synthesis, Characterization, and Reactivity Relevant to Catalytic Alkyne Hydroboration 钴硼基配合物：合成、表征及催化烷基硼化反应

IF 2.4 3区化学

Organometallics Pub Date : 2026-07-13 Epub Date: 2026-06-16 DOI: 10.1021/acs.organomet.6c00148

Anthony L. Amaya, Hadi D. Arman and Zachary J. Tonzetich*,

{"title":"Cobalt Boryl Complexes: Synthesis, Characterization, and Reactivity Relevant to Catalytic Alkyne Hydroboration","authors":"Anthony L. Amaya, Hadi D. Arman and Zachary J. Tonzetich*, ","doi":"10.1021/acs.organomet.6c00148","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00148","url":null,"abstract":"The synthesis and structure of several pincer-ligated cobalt boryl complexes is reported. These compounds include the cobalt(II) species, [Co(BE2)(CyPNP)] (E2 = pinacolato (pin) or catecholato (cat); CyPNP = anion of bis(dicyclohexylphosphinomethyl)pyrrole), as well as the formally cobalt(III) species, [Co(H)(BE2)(CyPNP)]. A rare cobalt diboryl complex has also been isolated through reaction of [Co(N2)(CyPNP)] with B2cat2. The reactivities of the new boryl species are investigated in migratory insertion reactions of unsaturated carbon substrates to investigate likely steps in hydroboration catalysis. The cobalt(II) compounds are found to readily insert both alkynes and allenes resulting in new organometallic species. Catalytic trials with the cobalt complexes demonstrate good activity for alkyne hydroboration, although mechanistic studies implicate a pathway involving a Co(I)/Co(III) cycle as opposed to direct involvement of Co(II) boryl species. The crystallographic structures of several of the new cobalt boryl compounds are reported.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 13","pages":"1591–1599"},"PeriodicalIF":2.4,"publicationDate":"2026-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148441737","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}

引用次数: 0

Metal-Mediated Reductive-Coupling of 2-Ethynylpyridine to Cluster-Bound 1,3-Functionalized Allenes 金属介导的2-乙基吡啶与团簇结合的1,3功能化烯的还原偶联

IF 2.4 3区化学

Organometallics Pub Date : 2026-07-13 Epub Date: 2026-06-13 DOI: 10.1021/acs.organomet.6c00145

Md. Tuhinur R. Joy, Israt Jahan, Jagodish C. Sarker*, Vladimir N. Nesterov, Graeme Hogarth* and Shariff E. Kabir*,

{"title":"Metal-Mediated Reductive-Coupling of 2-Ethynylpyridine to Cluster-Bound 1,3-Functionalized Allenes","authors":"Md. Tuhinur R. Joy, Israt Jahan, Jagodish C. Sarker*, Vladimir N. Nesterov, Graeme Hogarth* and Shariff E. Kabir*, ","doi":"10.1021/acs.organomet.6c00145","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00145","url":null,"abstract":"Reductive-coupling of 2-ethynylpyridine (HC≡C-py, py = 2-NC5H4) upon reaction with [Os3(CO)8(μ-H)2(μ-dppm)] (1) affords three isomeric clusters containing 1,3-functionalized allene ligands, namely [Os3(CO)7(μ-dppm){μ3,κ1(N)κ1(N)-pyC(Me)CC(H)py}] (2) and [Os3(CO)7(μ-dppm){μ3,κ1(N)κ1(N)-pyCH2CHCC(H)py}] (3-4) which have been separated and characterized by single crystal X-ray diffraction studies. Each contains an open 50-electron triosmium framework, the functionalized allene ligand acting as an 8-electron donor via coordination of three carbons and the two pyridyl nitrogens. Cluster 2 contains a trisubstituted allene, while 3 and 4 (which interconvert) contain disubstituted allenes. DFT studies have been used to assess their relative energies. They are proposed to result from initial migratory alkyne insertion into a hydride, leading to competitive formation of either α– and β–alkenyl complex, followed by insertion of a second hydride to afford mono- or disubstituted alkylidenes, which react with a second equivalent of 2-ethynylpyridine, likely following its conversion to a metal-bound vinylidene.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 13","pages":"1582–1590"},"PeriodicalIF":2.4,"publicationDate":"2026-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.6c00145","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148441487","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}

引用次数: 0