Organometallics最新文献

{"title":"Thioamidinate Zinc Complexes: Synthesis and Photoluminescence Studies","authors":"Shubham,&nbsp;Mohd Iqbal,&nbsp;Vanitha R. Naina and Peter W. Roesky*,&nbsp;","doi":"10.1021/acs.organomet.6c00149","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00149","url":null,"abstract":"<p >Thioamidinate Zn(II) complexes have been of great interest in chemical vapor deposition (CVD) due to their sufficient volatility; however, their photophysical properties remain largely unexplored. Here, a phenyl- and <i>tert</i>-butyl-substituted thioamidinate ligand (<b>L</b>) has been employed for the synthesis of Zn(II) complexes. Reactions with different Zn(II) precursors like [ZnMe₂(TMEDA)] (TMEDA = tetramethylethylenediamine), [ZnPh₂] and [{ATI(<i>i</i>-Pr)₂}Zn–N(TMS)₂] (ATI = aminotroponiminato, TMS = trimethylsilyl), afforded complexes of the type [<b>L</b>₂Zn(TMEDA)], [<b>L</b>₄Zn₂] and [<b>L</b>Zn{ATI(<i>i</i>-Pr)₂}], respectively. The resulting Zn(II) complexes exhibit phosphorescence with emission maxima ranging from 490 to 560 nm at 77 K, while ranging from 435 to 550 nm at 295 K.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 13","pages":"1600–1607"},"PeriodicalIF":2.4,"publicationDate":"2026-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148441884","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":"Flash Communication: Reaction of a Yttrium Phosphide Complex with Carbon Dioxide Gives a Paddlewheel-Like Phosphinocarboxylate","authors":"Hannah S. Redmill,&nbsp;George F. S. Whitehead and David P. Mills*,&nbsp;","doi":"10.1021/acs.organomet.6c00173","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00173","url":null,"abstract":"<p >The insertion of carbon dioxide into rare earth metal–phosphorus bonds is underexplored compared to many other rare earth metal–ligand σ-bonds. Treatment of a C₆D₆ solution of the dimeric yttrium bis(trimethylsilyl)phosphide complex [Y(P″)₂(μ-P″)]₂ (<b>1-Y</b>; P″ = {P(SiMe₃)₂}⁻) with 1 atm carbon dioxide resulted in rapid conversion to the dimeric hexaphosphinocarboxylate product [Y{O₂C(P″)-κ²<i>O</i>,<i>O</i>′}{μ-O₂C(P″)-1κ<i>O</i>;2κ<i>O</i>′}{μ-O₂C(P″)-1:2κ²<i>O</i>;1κ<i>O</i>′}]₂ (<b>2-Y</b>), which was characterized by single crystal X-ray diffraction, multinuclear NMR and ATR-IR spectroscopy, and elemental analysis. Complex <b>2-Y</b> has a paddlewheel-like structure, with one bidentate bis(silyl)phosphinocarboxylate terminally bound at each yttrium center and the other four ligands bridging these ions with two distinct binding modes. This dimeric formulation persists in solution, with dynamic averaging of bridging ligand environments.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 13","pages":"1484–1488"},"PeriodicalIF":2.4,"publicationDate":"2026-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148441981","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":"Interpreting In-operando ESI-MS in Cu-Mediated C–H Carboxylation through Structural and Energetic Constraints","authors":"Isabella Ogilvy,&nbsp;Vladimir Gorbachev,&nbsp;Jonathan Martens,&nbsp;Jos Oomens,&nbsp;Giel Berden,&nbsp;Alexandra Tsybizova* and Peter Chen*,&nbsp;","doi":"10.1021/acs.organomet.6c00137","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00137","url":null,"abstract":"<p >In-operando electrospray ionization mass spectrometry (ESI-MS) is a powerful tool for investigating reaction mechanisms by monitoring ions directly from the reacting solution in real time. However, observations based on <i>m</i>/<i>z</i> alone often do not constrain mechanistic assignments uniquely. Here we examine the interpretive limits of in-operando ESI-MS using copper-mediated carboxylation chemistry as a case study. Complementary characterization by collision-induced dissociation (CID), threshold CID energetics, infrared multiple-photon dissociation spectroscopy, and density-functional theory reveals that the dominant ion corresponds to an N-bound Cu–benzoxazole resting adduct rather than the Cu–C2 intermediate crystallographically characterized under stoichiometric conditions. Reinterpretation of the observed ions in light of these constraints establishes that the N-bound adduct is the genuine entry point into the productive catalytic cycle, and that the Cu–C2 intermediate─while chemically competent─does not accumulate under catalytic conditions, consistent with the principle that the most readily isolable intermediate is not necessarily the kinetically relevant one. This case study demonstrates that structural and energetic constraints are essential when using in-operando ESI-MS to investigate reaction mechanisms.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 13","pages":"1571–1581"},"PeriodicalIF":2.4,"publicationDate":"2026-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148442071","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 and Reactivity of Geometrically Constrained Methylaluminate Anionic Species","authors":"Dongmei Ran,&nbsp;Ruihao Huang,&nbsp;Heyang Gao,&nbsp;Min Li,&nbsp;Weilong Ji and Yuanting Su*,&nbsp;","doi":"10.1021/acs.organomet.6c00155","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00155","url":null,"abstract":"<p >The tetrahedral geometry of four-coordinate aluminum(III) complexes has long dominated aluminum coordination chemistry. Planarization via geometric constraint is predicted to enhance Lewis acidity, yet geometrically constrained aluminum anions remain exceedingly rare, and a methylaluminate variant has never been reported. Herein, we report the synthesis, structure, and reactivity of a geometrically constrained tetracoordinate methylaluminate anion. The T-shaped germanate(II) <b>K[</b>^<b>NNN</b><b>LGe:]</b> undergoes Ge-to-Al metathesis with AlMe₃ in THF, giving the square-pyramidal adduct <b>K[</b>^<b>NNN</b><b>LAlMe(THF)]</b>. Removal of THF under reduced pressure affords the dimer <b>{K[</b>^<b>NNN</b><b>LAlMe]}</b>_<b>2</b> with the τ₄ value of 0.43. This dimer reversibly binds THF, demonstrating Lewis acidity, and reacts with MeI to yield ^<b>NNN</b><b>LAlMe(DME)</b>.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 13","pages":"1477–1480"},"PeriodicalIF":2.4,"publicationDate":"2026-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148441481","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":"Unraveling the Origin of Chemo- and Enantioselectivity in Pd/GF-Phos-Catalyzed Asymmetric Three-Component Synthesis of Chiral Diarylmethyl Alkynes: A DFT Study","authors":"Jinning Yin,&nbsp;Bo Xiao*,&nbsp;Yonglan Peng,&nbsp;Xiaoyan Chen,&nbsp;Xiangzhuo Chen,&nbsp;Xiaoting Li* and Bin Li*,&nbsp;","doi":"10.1021/acs.organomet.6c00156","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00156","url":null,"abstract":"<p >Chiral diarylmethyl alkynes are valuable scaffolds in medicinal chemistry, yet their asymmetric synthesis remains a significant challenge. A recently developed Pd/GF-Phos-catalyzed three-component coupling of aryl bromides, diazo compounds, and terminal alkynes offers an efficient and enantioselective access to these targets. To elucidate the mechanism of this transformation, we performed comprehensive density functional theory (DFT) calculations. The results reveal that the carbenation reaction between the Pd(II) species and the diazo compound is the enantioselectivity-determining step, and the transmetalation of copper acetylide to the diarylmethyl-Pd(II)Br species is the rate-determining step. The observed enantioselectivity arises from a combination of <i>trans</i> effect and side arm effect of the GF-Phos ligand. Notably, the GF-Phos ligand exhibits remarkable structural adaptability, dynamically adjusting its coordination mode to promote both reactivity and selectivity across the catalytic cycle. This study also rationalizes the diminished reactivity of Ming-Phos, which arises from structural differences in its ligand backbone relative to GF-Phos. Collectively, these findings not only offer mechanistic insights but also suggest that effective ligand design may benefit from combining adaptive coordination behavior with a well-defined chiral environment for enantioinduction while avoiding the formation of overly stable Pd(0) resting states.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 13","pages":"1608–1615"},"PeriodicalIF":2.4,"publicationDate":"2026-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148441750","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":"Flash Communication: An Atomically Dispersed Cu Photocatalyst for the Synthesis of Trifluoromethylated Ferrocenes","authors":"Corentin Ludwig,&nbsp;Suman Pradhan,&nbsp;Alba Lomas Neff,&nbsp;Shoubhik Das*,&nbsp;Kevin Cariou* and Gilles Gasser*,&nbsp;","doi":"10.1021/acs.organomet.6c00140","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00140","url":null,"abstract":"<p >A recently developed photocatalytic trifluoromethylation method, with the atomically dispersed photocatalyst Cu-@f-gC₃N₄ and Togni I reagent as a −CF₃ source, was optimized for the functionalization of ferrocene. This photocatalytic reaction proceeded at room temperature under visible-light irradiation, and this functionalization remained compatible with functional groups such as ether and halogens.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 13","pages":"1473–1476"},"PeriodicalIF":2.4,"publicationDate":"2026-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148441754","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":"Influence of Identity and Position of Ligand Substituents on Tris(amido) Yttrium Complexes","authors":"Sofie K. Hokanson,&nbsp;Rana B. Abdu,&nbsp;Elena Álvarez-Ruiz and Courtney C. Roberts*,&nbsp;","doi":"10.1021/acs.organomet.6c00124","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00124","url":null,"abstract":"<p >Early transition metals have been reported to be effective C(sp³)-C(sp³) cross-coupling catalysts when paired with tris(amido) redox-active ligands. We developed a series of ligands to probe the effects of radical-stabilizing groups and substituent position on yttrium tris(amido) complexes. We synthesized neutral yttrium complexes <b>1-Y–3-Y</b> which were characterized via NMR spectroscopy, single-crystal X-ray crystallography, cyclic voltammetry, and UV–vis spectroscopy. Single electron-oxidized complexes <b>1-Y</b>_<b>ox</b><b>–3-Y</b>_<b>ox</b>, which are relevant catalytic intermediates, were also synthesized and characterized via NMR, EPR, and UV–vis/NIR spectroscopy. DFT calculations were used to further elucidate the electronic structures of <b>1-Y–3-Y</b> and <b>1-Y</b>_<b>ox</b><b>–3-Y</b>_<b>ox</b>. Complexes <b>1-Y–3-Y</b> were used as catalysts in a C(sp³)-C(sp³) cross-coupling reaction, and initial rates were used to determine the influence of the substituents on catalysis. The results indicate that substituent identity and placement impact the electronic structure of the complexes but have minor effects on catalysis.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 13","pages":"1528–1534"},"PeriodicalIF":2.4,"publicationDate":"2026-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148441916","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":"Organolanthanide Thermolysis Generates Ln/Al Tuck-Over Complexes and a 9,10-Dialumina-9,10-dihydroanthracenide Derivative","authors":"Gernot T. L. Zug,&nbsp;Martin Bonath,&nbsp;Georgios Spiridopoulos,&nbsp;Felix Vöhringer,&nbsp;Cäcilia Maichle-Mössmer,&nbsp;Peter Sirsch* and Reiner Anwander*,&nbsp;","doi":"10.1021/acs.organomet.6c00129","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00129","url":null,"abstract":"<p >The synthesis of two new organoaluminum stabilized rare-earth-metal phenyl motifs is reported, featuring heterobimetallic Ln/Al tuck-over complexes Cp*Ln[C₅Me₄(CH₂Al(μ–Ph)Ph₂)] (Cp* = C₅Me₅, Ln = Y, La, Lu) and 9,10-dialumina-9,10-dihydroanthracenido derivatives Cp*Ln[(μ-C₆H₄)₂Al₂(μ–Ph)Ph₃] (Ln = Y, Lu). Prolonged thermal treatment of Cp*₂Ln(AlMe₄) (Ln = Y, La, Lu) in benzene leads to stepwise methyl/phenyl exchange and then metalation of a Cp* methyl group and concomitant elimination of benzene to yield Ln/Al tuck-over complexes Cp*Ln[C₅Me₄(CH₂Al(μ-Ph)Ph₂)]. Isolated Cp*₂Ln(AlPh₄) (Ln = Y, La) also reacts to Cp*Ln[C₅Me₄(CH₂Al(μ-Ph)Ph₂)] at elevated temperatures. Treatment of Cp*Ln[C₅Me₄(CH₂Al(μ-Ph)Ph₂)] (Ln = Y, Lu) with AlMe₃ results in a reverse phenyl/methyl exchange. THF breaks the Y–C(phenyl) bond in Cp*Y[C₅Me₄(CH₂Al(μ-Ph)Ph₂)] yielding zwitterionic complex Cp*Y(thf)₂[C₅Me₄(CH₂AlPh₃)]. The 9,9,10,10-tetraphenyl-9,10-dialumina-9,10-dihydroanthracenido derivatives Cp*Ln[(μ-C₆H₄)₂Al₂(μ–Ph)Ph₃] (Ln = Y, Lu) are either formed as very minor byproducts in the reaction of Cp*₂Ln(AlMe₄) with benzene or upon treatment of the benzyl compounds Cp*Ln(CH₂C₆H₄NMe₂-<i>o</i>)₂ with 5–6 equiv AlPh₃. Mixed methyl/phenyl complexes Cp*₂Lu(Me₂AlPh₂), Cp*₂La(MeAlPh₃), and phenyl complex Cp*₂La(AlPh₄) were isolated from the methyl/phenyl exchange sequence when heating Cp*₂Ln(AlMe₄) in benzene. Such thermally controlled benzene elimination from phenylaluminate complexes as highlighted by new structural motifs does not only extend rare-earth-metal phenyl chemistry but might inspire future investigations into inert bond activation with organolanthanide moieties at elevated temperatures.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 13","pages":"1541–1553"},"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.6c00129","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148441570","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":"Effects of Alkyne Substituents and X-Ligands on Alkyne Insertion Reactions of RuHX(CO)(PPh3)3","authors":"Chun Wai Tang,&nbsp;Wenwei Qin,&nbsp;Wan Chak Lee,&nbsp;Ho Chuen Wan,&nbsp;Fu Kit Sheong,&nbsp;Herman H. Y. Sung,&nbsp;Ian D. Williams,&nbsp;Zhenyang Lin* and Guochen Jia*,&nbsp;","doi":"10.1021/acs.organomet.5c00511","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00511","url":null,"abstract":"<p >The reactions of diaryl alkynes ArC≡CAr with RuHX(CO)(PPh₃)₃ (X = F, Cl, Br, I, H, N₃, NCS, CN) were investigated. The halide complexes RuHX(CO)(PPh₃)₃ (X = Cl, Br, I) undergo alkyne insertion reactions with the diaryl alkynes ArC≡CAr (Ar = <i>p</i>-C₆H₄OMe, Ph, <i>p</i>-C₆H₄CO₂Me) at room temperature to afford alkenyl complexes RuX(ArC═CHAr)(CO)(PPh₃)₂. A substituent effect was observed, with alkynes bearing electron-withdrawing groups displaying higher reactivity. The insertion reaction is also strongly influenced by the X-ligands. The rate of the alkyne insertion of the halide complexes follows the order of Cl &lt; Br &lt; I. In contrast, complexes bearing the π-donor F, the purely σ-donor H, and π-acceptors such as N₃, NCS, and CN, exhibit significantly reduced reactivity toward alkyne insertion with ArC≡CAr under ambient conditions. Density functional theory calculations reveal that phosphine dissociation, leading to the formation of a five-coordinate intermediate RuHX(CO)(PPh₃)₂, and subsequent alkyne coordination are two key steps governing the overall reactivity. These steps are influenced by the steric and electronic properties of the X-ligands, as well as the alkyne substituents.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 13","pages":"1489–1500"},"PeriodicalIF":2.4,"publicationDate":"2026-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148441904","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":"A 3-Fluoropyridine-Substituted Grubbs III Catalyst as a 19F NMR Probe for Chain Chelation in ROMP","authors":"Björn Grabbet,&nbsp;Martin Lutz and Arnaud Thevenon*,&nbsp;","doi":"10.1021/acs.organomet.6c00085","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00085","url":null,"abstract":"<p >Propagation rates in ruthenium-catalyzed ring-opening metathesis polymerization (ROMP) can be attenuated by the transient coordination of the growing chain to the metal center. Direct spectroscopic observation of such chelation under catalytically relevant conditions remains challenging, owing to the fast exchange dynamics of propagating intermediates and spectral overlap in conventional ¹H NMR. Here, we report a third-generation Grubbs catalyst (<b>GIII</b>) in which the ancillary pyridine is substituted with 3-fluoropyridine (<b>F-GIII</b>), such that chain chelation may be observed using variable-temperature ¹⁹F nuclear magnetic resonance (VT-NMR) spectroscopy. <b>F-GIII</b> is readily prepared analogously to <b>GIII</b> from <b>GII</b>, giving a solid-state structure closely related to its 3-bromopyridine analogue, and exhibits comparable reactivity. A selection of chelation-prone or nonchelating norbornene- and oxanorbornene-based monomers is investigated using ¹⁹F VT NMR and displays either well-defined temperature-dependent equilibria between coordinated and dissociated pyridine or persistent dissociation consistent with chelating behavior. These results establish ¹⁹F NMR as a convenient, noninvasive, and direct probe for studying growing polymer chain-catalyst interactions during ROMP.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 13","pages":"1513–1519"},"PeriodicalIF":2.4,"publicationDate":"2026-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148441944","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}