Organometallics最新文献_第6页

Germanium-Functionalized Tri- and Tetraphosphido Cobalt Complexes 锗功能化三磷和四磷钴配合物

IF 2.9 3区化学

Organometallics Pub Date : 2025-07-31 DOI: 10.1021/acs.organomet.5c00214

Karolina Trabitsch, Sebastian Hauer, Gábor Balázs, Jan J. Weigand and Robert Wolf*,

{"title":"Germanium-Functionalized Tri- and Tetraphosphido Cobalt Complexes","authors":"Karolina Trabitsch, Sebastian Hauer, Gábor Balázs, Jan J. Weigand and Robert Wolf*, ","doi":"10.1021/acs.organomet.5c00214","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00214","url":null,"abstract":"We report the synthesis of germanium-containing polyphosphorus ligands in transition metal complexes through the insertion of an Ar′GeCl unit into a P–P bond of polyphosphorus ligands (Ar′ = 2,6-(2,6-iPr2C6H3)2-C6H3). Germatetraphosphido complexes [(L)Co(η4-P4GeAr′)] (1a: L = PHDI; 1b: L = Ar*BIAN; PHDI = bis(2,6-diisopropylphenyl)phenanthrene-9,10-diimine, Ar*BIAN = 1,2-bis(arylimino)acenaphthene, aryl = 2,6-dibenzhydryl-4-isopropylphenyl) were obtained by treatment of the anionic cyclo-P4 complexes [K(18c-6)][(L)Co(η4-P4)] with [Ar′GeCl]2 . Similar reactions of the cyclo-P3 complexes [cat][(L)Co(CN)(η3-P3)] ([cat]+ = [nBu4N]+ or [K(18c-6)]+) afforded [cat][(L)Co(η3-P3GeAr′Cl)(CN)] (2a: L = PHDI, [cat]+ = [nBu4N]+; 2b: L = Ar*BIAN, [cat]+ = [K(18c-6)]+). The reactivity of 2a was studied toward group 14 electrophiles, yielding neutral germatriphosphido analogues [(PHDI)Co(η3-P3GeAr′Cl)(CNER3)] (3-ER3, ER3 = CPh3, Si(iPr)3). Furthermore, treatment of 2a with the group 13 Lewis acid GaCl3 gave [nBu4N][(PHDI)Co(η3-P3GeAr′Cl)(CNGaCl3)] (4-Ga) and [(PHDI)Co(η3-P2Ge(PAr′))(CNGaCl3)] (5-Ga), which features a remarkable P3GeAr′ ligand. Compounds 1–5 were isolated as crystalline materials and characterized by single-crystal X-ray diffraction and multinuclear NMR spectroscopy supported by DFT calculations.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 15","pages":"1721–1727"},"PeriodicalIF":2.9,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00214","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144807657","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

Water-Driven Isomerization Control: Dinuclear Cobalt-Catalyzed Monoisomerization of Linear Terminal Alkenes 水驱动异构化控制：双核钴催化线性末端烯烃的单异构化

IF 2.9 3区化学

Organometallics Pub Date : 2025-07-31 DOI: 10.1021/acs.organomet.5c00131

Gao-Yin Wang, Hongdan Zhu, Yuyang Xu, Ke Chen, Jiayi Lin, Qian Peng* and Xiaoming Wang*,

引用次数: 0

Flash Communication: On “Ag[BArF4]” and an Expedient Synthesis of [Ag(C6H6)3][BArF4] 闪光通信：“Ag[BArF4]”及[Ag(C6H6)3][BArF4]的便捷合成

IF 2.9 3区化学

Organometallics Pub Date : 2025-07-31 DOI: 10.1021/acs.organomet.5c00170

Alex McSkimming*,

引用次数: 0

Cobalt-Catalyzed Hydrogermylation of Nonactivated Alkenes Enabled by Photoirradiation 光催化非活化烯烃的钴氢胚芽化反应

IF 2.9 3区化学

Organometallics Pub Date : 2025-07-31 DOI: 10.1021/acs.organomet.5c00237

Peihao Wang, Dongyang Wang* and Liang Deng*,

引用次数: 0

Dynamic Effects Influencing Mechanisms and Selectivity in Metal-Mediated Organometallic Reactions 影响金属介导的有机金属反应机制和选择性的动力学效应

IF 2.9 3区化学

Organometallics Pub Date : 2025-07-30 DOI: 10.1021/acs.organomet.5c00162

Anthony J. Schaefer, Jyothish Joy, Michael T. Davenport and Daniel H. Ess*,

{"title":"Dynamic Effects Influencing Mechanisms and Selectivity in Metal-Mediated Organometallic Reactions","authors":"Anthony J. Schaefer, Jyothish Joy, Michael T. Davenport and Daniel H. Ess*, ","doi":"10.1021/acs.organomet.5c00162","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00162","url":null,"abstract":"For organometallic reactions it has now become routine to calculate the molecular energy of stationary structures and stitch them together as a potential energy surface. This surface generally defines the reaction mechanism and is used to evaluate selectivity based on statistical transition-state theory. Recent computational studies have demonstrated that some organometallic reactions have nonstatistical behavior or dynamic effects where atomic motion plays a key role in the reaction mechanism and selectivity. The most tractable and straightforward method of identifying and demonstrating nonstatistical dynamic effects in organometallic reactions is the use of molecular dynamics simulations, which provides time-resolved atomic motion as reactions proceed. This tutorial provides examples of potential energy surfaces where molecular dynamics simulations are likely needed to understand and evaluate the reaction mechanism and selectivity. There is a concise overview of key concepts and issues when using and interpreting molecular dynamics simulations for organometallic reactions. Several key examples are highlighted to illustrate a variety of dynamic effects that have been identified in organometallic reactions.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 15","pages":"1603–1619"},"PeriodicalIF":2.9,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144807351","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

Correction to “Little MAO: Isolation of an {Al4} Methylalumoxane Species from the Reaction of Trimethylaluminum with Water” 对“小毛：从三甲基铝与水的反应中分离出{Al4}甲基铝氧烷”的更正

IF 2.9 3区化学

Organometallics Pub Date : 2025-07-30 DOI: 10.1021/acs.organomet.5c00266

Tassilo Berger, Markus Kramer, Cäcilia Maichle-Mössmer and Reiner Anwander*,

引用次数: 0

Flash Communication: Multinuclear Zwitterionic Germylene with Ge4 Chain Motif 闪烁通信：多核两性离子锗烯与Ge4链基序

IF 2.9 3区化学

Organometallics Pub Date : 2025-07-29 DOI: 10.1021/acs.organomet.5c00118

Jicheng Wang, Sonam Suthar, Ming Li, Manbo Zhang, Kartik Chandra Mondal*, Hongping Zhu* and Bin Li*,

引用次数: 0

Photophysics and Dynamics of Tautomerization in Two-Coordinate Carbene-Metal-Amide Complexes 二坐标碳-金属-酰胺配合物中互变异构的光物理和动力学

IF 2.9 3区化学

Organometallics Pub Date : 2025-07-29 DOI: 10.1021/acs.organomet.5c00150

Ao Jiao, Leander Spierling, Shawn Wagner, Peter I. Djurovich and Mark E. Thompson*,

{"title":"Photophysics and Dynamics of Tautomerization in Two-Coordinate Carbene-Metal-Amide Complexes","authors":"Ao Jiao, Leander Spierling, Shawn Wagner, Peter I. Djurovich and Mark E. Thompson*, ","doi":"10.1021/acs.organomet.5c00150","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00150","url":null,"abstract":"A series of Au(I) carbene-metal-amide (cMa) complexes using N-heterocyclic carbenes and N-benzo[d]benzo[4,5]imidazo[1,2-a]imidazolyl (bim) amide ligands have been synthesized as models to investigate coordination tautomerization in cMa compounds. Methyl substituents on the bim ligand were used to increase steric hindrance and break the degeneracy of tautomers. The presence of tautomers was identified using X-ray crystallography and 1H NMR spectroscopy, and the kinetics of tautomerization were measured. The dimethylbim (DMbim) ligand in cMa complexes thermodynamically favors a specific tautomer and suppresses the rate of tautomerization. The steric bulk of the NHC carbene and amide ligands and metal-carbene bond strength were found to alter the tautomerization rate. The photophysical properties of DMbim-based cMa are comparable to their bim-based analogs. The DMbim-based cMa complexes exhibit short emission lifetimes (τ = 200 ns) and fast radiative rates (kr = 4.9 × 106 s–1) with high photoluminescent quantum yields (ΦPL = 98%). Analysis of the temperature-dependent photophysical properties indicates fast lifetimes for the singlet state (τ = 14 ns) with small exchange energies (ΔEST ∼ 40 meV). The compounds provide general insight for rational molecular designs to suppress tautomerization.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 15","pages":"1670–1678"},"PeriodicalIF":2.9,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144807422","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

IF 2.5 3区化学

Organometallics Pub Date : 2025-07-28

引用次数: 0

IF 2.5 3区化学

Organometallics Pub Date : 2025-07-28

Tassilo Berger, Markus Kramer, Cäcilia Maichle-Mössmer and Reiner Anwander*,

引用次数: 0