Organometallics最新文献_第10页

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-12 DOI: 10.1021/acs.organomet.4c0038810.1021/acs.organomet.4c00388

Patricio Castillo, Bryan J. Foley, Samuel R. Lee, Billy J. McCulloch, Nattamai Bhuvanesh and Oleg V. Ozerov*,

{"title":"Synthesis of Os Hydride Complexes Supported by the Diarylamido/Bis(phosphine) PNP Ligand and Attempts at Using (PNP)Ru and (PNP)Os Complexes in C–H Borylation Catalysis","authors":"Patricio Castillo, Bryan J. Foley, Samuel R. Lee, Billy J. McCulloch, Nattamai Bhuvanesh and Oleg V. Ozerov*, ","doi":"10.1021/acs.organomet.4c0038810.1021/acs.organomet.4c00388","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00388https://doi.org/10.1021/acs.organomet.4c00388","url":null,"abstract":"This manuscript describes the synthesis of Os complexes supported by the diarylamido/bis(phosphine) PNP pincer ligand. Compound (PNP)OsH(CO) (3-Os) was prepared by analogy with the previously reported 3-Ru. However, attempts to make (PNP)OsH3 (4-Os) analogously to 4-Ru resulted in the formation of an unexpected compound (5-Os) that is a product of addition of a BH3 unit across the Os–N bond in 4-Os. Nonetheless, 4-Os was prepared via an alternative route. Unlike 4-Ru, 4-Os appears to be a classical trihydride. Compounds 3-Ru, 3-Os, 4-Os, 4-Ru, and 5-Os were tested as potential catalysts for (a) dehydrogenative borylation of terminal alkynes (DHBTA) and (b) dehydrogenative borylation of benzene. No catalytic C–H borylation was observed for any of them, but all of them catalyzed unselective hydroboration of 4-MeC6H4CCH.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 22","pages":"2944–2950 2944–2950"},"PeriodicalIF":2.5,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00388","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694597","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

Impact of the N-Heterocyclic Carbene (NHC) Ligand on the trans-[Pd(NHC)(NH2nBu)Cl2] Precatalyst Architecture in C–N Bond-Forming Reactions N-Heterocyclic Carbene (NHC) 配体对反式-[Pd(NHC)(NH2nBu)Cl2]前催化剂结构在 C-N 成键反应中的影响

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-11 DOI: 10.1021/acs.organomet.4c0041910.1021/acs.organomet.4c00419

Nestor Bracho Pozsoni, Fady Nahra, Kristof van Hecke, Catherine S. J. Cazin* and Steven P. Nolan*,

引用次数: 0

Predictive Models for Ligand Effects on a Reactive Al-Containing Radical Intermediate from Multivariate Linear Regression Analysis 从多元线性回归分析得出配体对含铝活性自由基中间体影响的预测模型

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-11 DOI: 10.1021/acs.organomet.4c0028510.1021/acs.organomet.4c00285

S. M. Supundrika Subasinghe, Maxim R. Radzhabov and Neal P. Mankad*,

{"title":"Predictive Models for Ligand Effects on a Reactive Al-Containing Radical Intermediate from Multivariate Linear Regression Analysis","authors":"S. M. Supundrika Subasinghe, Maxim R. Radzhabov and Neal P. Mankad*, ","doi":"10.1021/acs.organomet.4c0028510.1021/acs.organomet.4c00285","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00285https://doi.org/10.1021/acs.organomet.4c00285","url":null,"abstract":"Our lab has studied a complex with an Al–Fe bond capable of cooperative substrate activation processes. This reactivity was previously found to depend on Al–Fe homolytic bond dissociation followed by substrate coordination to the AlIII center of the resulting redox noninnocent radical intermediate. The current study investigates ligand influences on the Al–Fe bond dissociation free energy (BDFEAl–Fe) and the Gibbs free energy of H2O coordination at aluminum (ΔGOH2) for a series of variants with systematic changes in their ligand substitution patterns. DFT calculations combined with multivariate linear regression analysis provided predictive models for ligand effects on both BDFEAl–Fe and ΔGAl–OH2 for three synthetically tunable positions in the molecular architecture when using appropriate electronic (σpara, σmeta) and steric (wSterimol, %Vbur) descriptors. Chemical interpretations of the predictive models were facilitated by the use of these intuitive descriptors. Linear scaling relationships relating BDFEAl–Fe and ΔGOH2 provided further insight. We expect our findings to inform designs of future Al-containing heterobinuclear complexes for small molecule activation processes and cleavage reactions of strong or inert bonds.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 22","pages":"2854–2861 2854–2861"},"PeriodicalIF":2.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694459","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

Synthesis and Catalytic Application of Ru(II) Complexes Supported by Zwitterionic Triazol(in)ium-5-dithiocarboxylates (MIC·CS2) and Isothiocyanates (MIC·CSNPh) 5-二硫代羧酸三氮唑(in)矾盐 (MIC-CS2) 和异硫氰酸盐 (MIC-CSNPh) 支持的 Ru(II) 配合物的合成与催化应用

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-07 DOI: 10.1021/acs.organomet.4c0036410.1021/acs.organomet.4c00364

Amador Flores-Ávila, Emmanuel Campos-Dominguez, Adi J. Martínez-Martell, Francisco J. Ruiz-Mendoza, Cesar I. Sandoval-Chávez and Daniel Mendoza-Espinosa*,

{"title":"Synthesis and Catalytic Application of Ru(II) Complexes Supported by Zwitterionic Triazol(in)ium-5-dithiocarboxylates (MIC·CS2) and Isothiocyanates (MIC·CSNPh)","authors":"Amador Flores-Ávila, Emmanuel Campos-Dominguez, Adi J. Martínez-Martell, Francisco J. Ruiz-Mendoza, Cesar I. Sandoval-Chávez and Daniel Mendoza-Espinosa*, ","doi":"10.1021/acs.organomet.4c0036410.1021/acs.organomet.4c00364","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00364https://doi.org/10.1021/acs.organomet.4c00364","url":null,"abstract":"In recent years, NHC-derived zwitterions [NHC·CS(X)] (X = S and NR) have gained a great deal of attention owing to their various applications in fields such as organic synthesis, organometallics, and more recently in catalysis. In this work, we report that the reaction of free triarylated triazol-5-ylidenes (MIC) with equimolar amounts of dithiocarboxylate and isothiocyanate derivatives allows for the preparation of a series of MIC·SC2 and MIC·CSNAr zwitterions in good yields. Their potential as ligands for transition metals was demonstrated by the synthesis of ruthenium(II) complexes with the general formulas [RuCl(p-cymene)(MIC·CS2)]PF6 and [RuCl(p-cymene)(MIC·CNSAr)]PF6. The zwitterions and the ruthenium complexes were fully characterized by NMR spectroscopy, X-ray crystallography, TGA, and elemental analysis. The new ruthenium complexes were successfully applied as catalysts in the transfer hydrogenation of a series of aldehydes and ketones showing good efficiency under low catalyst loadings and providing excellent conversions.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 22","pages":"2926–2934 2926–2934"},"PeriodicalIF":2.5,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694440","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

Synthesis and Structural Investigation of Rigid Naphthyridine-Bis(carbene) for Trigonal Planar Coordination of Coinage Metals

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-07 DOI: 10.1021/acs.organomet.4c0038310.1021/acs.organomet.4c00383

Evan A. Patrick, Jeremy D. Erickson, R. Morris Bullock and Ba L. Tran*,

{"title":"Synthesis and Structural Investigation of Rigid Naphthyridine-Bis(carbene) for Trigonal Planar Coordination of Coinage Metals","authors":"Evan A. Patrick, Jeremy D. Erickson, R. Morris Bullock and Ba L. Tran*, ","doi":"10.1021/acs.organomet.4c0038310.1021/acs.organomet.4c00383","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00383https://doi.org/10.1021/acs.organomet.4c00383","url":null,"abstract":"Coinage metal complexes, particularly Cu(I) and Au(I), supported by N-heterocyclic carbenes are of broad interest in organometallic synthesis, catalysis, and luminescent materials. The d10 coinage metals can adopt varied linear, trigonal planar, and tetrahedral geometries. However, two-coordinate, linear Cu(I) and Au(I) complexes supported by sterically demanding monodentate or chelating carbenes are generally observed. In most cases, chelating ligands generate multinuclear species with linear geometries at the corresponding Cu(I) centers rather than mononuclear complexes. In this report, we synthesized two bis(carbene) ligands anchored by a flexible bipyridine and a rigid naphthyridine backbone with tunable proximal and distal steric properties at the wingtips to examine the influence of backbone rigidity and directionality of carbene donors on the formation of trigonal planar coinage metal species. The bipyridine-bis(carbene) (ImPy)2 ligand exclusively stabilizes dinuclear chloride complexes of Cu(I) and Ag(I), whereas the naphthyridine-bis(carbene) (NBC) stabilizes mononuclear, trigonal planar chloride complexes of Cu(I) and Ag(I) and a dinuclear chloride Au(I) complex.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 2","pages":"373–384 373–384"},"PeriodicalIF":2.5,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091841","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: High-Pressure Synthesis and Post-synthetic Elimination of N2 Molecule of the Chromium Dinitrogen Complex, [Cr(PCy3)2(CO)3(N2)]

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-06 DOI: 10.1021/acs.organomet.4c0037310.1021/acs.organomet.4c00373

Kaiji Uchida*, Taku Kitayama, Shunya Tanaka, Shuta Adachi, Hiroaki Iguchi, Ryota Sakamoto and Shinya Takaishi*,

{"title":"Flash Communication: High-Pressure Synthesis and Post-synthetic Elimination of N2 Molecule of the Chromium Dinitrogen Complex, [Cr(PCy3)2(CO)3(N2)]","authors":"Kaiji Uchida*, Taku Kitayama, Shunya Tanaka, Shuta Adachi, Hiroaki Iguchi, Ryota Sakamoto and Shinya Takaishi*, ","doi":"10.1021/acs.organomet.4c0037310.1021/acs.organomet.4c00373","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00373https://doi.org/10.1021/acs.organomet.4c00373","url":null,"abstract":"Dinitrogen complexes have garnered significant attention due to their potential applications across various fields. The synthesis and characterization of novel dinitrogen complexes are essential to advancing this area of research. In this study, we report the bulk synthesis and first successful single crystal X-ray structure analysis of [Cr(PCy3)2(CO)3(N2)] using high-pressure nitrogen at 50 atm. The presence of the nitrogen ligand was confirmed by infrared (IR) spectroscopy and elemental analysis, and the interesting disorder phenomenon between N2 and CO ligands was also observed. The elimination process of the N2 ligand was monitored by a combination of thermogravimetry (TG) and temperature-programmed desorption (TPD), and the changes in the color, IR spectrum, and UV–vis spectrum of the complexes before and after elimination were investigated. These experimental results agree well with the results of density functional theory (DFT) calculations.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 3","pages":"459–463 459–463"},"PeriodicalIF":2.5,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371781","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

Design Principles for Activating Organohalides with Hydrogen-Derived Electrons 利用氢衍生电子激活有机卤化物的设计原则

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-05 DOI: 10.1021/acs.organomet.4c0036010.1021/acs.organomet.4c00360

Kaho Yamada, Yuu Kajiwara, Takeshi Yatabe, Ki-Seok Yoon, Hidetaka Nakai and Seiji Ogo*,

引用次数: 0

Iron-Catalyzed Synthesis of Ferrocenyl–Thioether Conjugates via C–S Cross-Coupling of Thioethers and Vinylic Chlorides: Construction, Anticancer, and Computational Studies 通过硫醚和乙烯基氯化物的 C-S 交叉偶合铁催化合成二茂铁基硫醚共轭物：构建、抗癌和计算研究

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-04 DOI: 10.1021/acs.organomet.4c0033010.1021/acs.organomet.4c00330

Vijesh Tomar, Deepak Sharma, Parveen Kumar, Deepika Sharma, Tejveer Singh, Meena Nemiwal* and Raj Kumar Joshi*,

{"title":"Iron-Catalyzed Synthesis of Ferrocenyl–Thioether Conjugates via C–S Cross-Coupling of Thioethers and Vinylic Chlorides: Construction, Anticancer, and Computational Studies","authors":"Vijesh Tomar, Deepak Sharma, Parveen Kumar, Deepika Sharma, Tejveer Singh, Meena Nemiwal* and Raj Kumar Joshi*, ","doi":"10.1021/acs.organomet.4c0033010.1021/acs.organomet.4c00330","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00330https://doi.org/10.1021/acs.organomet.4c00330","url":null,"abstract":"Herein, a library of ferrocenyl–thioether derivatives of acrylaldehyde and acrylonitrile is developed via a direct C–S bond formation reaction under mild conditions. Various aromatic and aliphatic thiols were successfully coupled with ferrocenyl acrylaldehyde/acrylonitrile in the presence of a chalcogen-stabilized iron–carbonyl cluster (Fe3Se2(CO)9). All the reactions were carried out in water under aerobic conditions, and the transformation of a wide range of ferrocenyl–thioether derivatives in good yields were obtained. Furthermore, cytotoxicity studies of some selected ferrocenyl–thioethers were performed against the prostate cancer cell line (PC-3) and normal human embryonic kidney cell line (HEK). 3-Ferrocenyl-3-(4-trifluoromethyl)-phenylsulfanyl was found to be significantly active. It showed an IC50 of 5.5 μM toward prostate cancer cell lines. Moreover, it also showed activity comparable to that of standard anticancer drugs including axitinib, nelfinavir, thymitaq, and (±) thioridazine. The anticancer activity was further supported by density functional theory calculations including the HOMO–LUMO energy gap, cyclic voltammetry, UV–vis studies, molecular docking, and reactive oxygen species analysis. All compounds synthesized in this report are new, and they may serve as milestones in the futuristic research of anticancer drugs.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 22","pages":"2882–2894 2882–2894"},"PeriodicalIF":2.5,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694558","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: Stopping the Movement of Carbon Atoms Traveling in Organic Molecules by Pinacolboryl Substituents 闪光交流：通过频哪醇硼酰取代基阻止碳原子在有机分子中的移动

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-04 DOI: 10.1021/acs.organomet.4c0034410.1021/acs.organomet.4c00344

Tamotsu Takahashi*, Masayoshi Bando, Hui Chen, Yang Zheng and Zhiyi Song*,

引用次数: 0

Reversible C–CN Bond Cleavage by a Formal Dinickel(I) Hydride Cation 形式二镍钴(I)氢化物阳离子的可逆 C-CN 键裂解作用

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-01 DOI: 10.1021/acs.organomet.4c0034010.1021/acs.organomet.4c00340

Yu Cao, Neil A. Dodd, John Bacsa and Joseph P. Sadighi*,

引用次数: 0