Organometallics最新文献

{"title":"IPr# Complexes─Highly-Hindered, Sterically-Bulky Cu(I) and Ag(I) N-Heterocyclic Carbenes: Synthesis, Characterization, and Reactivity","authors":"Greta Utecht-Jarzyńska*,&nbsp;Szymon Jarzyński,&nbsp;Md Mahbubur Rahman,&nbsp;Guangrong Meng,&nbsp;Roger Lalancette,&nbsp;Roman Szostak and Michal Szostak*,&nbsp;","doi":"10.1021/acs.organomet.4c0033310.1021/acs.organomet.4c00333","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00333https://doi.org/10.1021/acs.organomet.4c00333","url":null,"abstract":"<p >Metal–N-heterocyclic carbene (M–NHC) complexes are well-known as an important class of organometallic compounds widely used in transition-metal catalysis. Taking into account that the steric hindrance around the metal center is one of the major effects in M–NHC catalysis, the development of new, sterically hindered M–NHC complexes is an ongoing interest in this field of research. Herein, we report the synthesis and characterization of exceedingly sterically hindered, well-defined, air- and moisture-stable Cu(I) and Ag(I) complexes, [Cu(NHC)Cl] and [Ag(NHC)Cl], in the recently discovered IPr^# family of ligands that hinge upon modular peralkylation of anilines. The complexes in both the BIAN and IPr families of ligands are reported. X-ray crystallographic analyses and computational studies were conducted to determine steric effects, Frontier molecular orbitals, and bond orders. The complexes were evaluated in the model hydroboration of the alkynes. We identified [Cu(BIAN–IPr^#)Cl] and [Ag(BIAN–IPr^#)Cl] as highly reactive catalysts with the reactivity outperforming the classical IPr and IPr*. Considering the attractive features of well-defined Cu(I)–NHC and Ag(I)–NHC complexes, this class of sterically bulky yet wingtip-flexible complexes will be of interest for catalytic processes in various areas of organic synthesis and catalysis.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00333","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142450430","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":"IPr^# Complexes-Highly-Hindered, Sterically-Bulky Cu(I) and Ag(I) N-Heterocyclic Carbenes: Synthesis, Characterization, and Reactivity.","authors":"Greta Utecht-Jarzyńska, Szymon Jarzyński, Md Mahbubur Rahman, Guangrong Meng, Roger Lalancette, Roman Szostak, Michal Szostak","doi":"10.1021/acs.organomet.4c00333","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00333","url":null,"abstract":"<p><p>Metal-N-heterocyclic carbene (M-NHC) complexes are well-known as an important class of organometallic compounds widely used in transition-metal catalysis. Taking into account that the steric hindrance around the metal center is one of the major effects in M-NHC catalysis, the development of new, sterically hindered M-NHC complexes is an ongoing interest in this field of research. Herein, we report the synthesis and characterization of exceedingly sterically hindered, well-defined, air- and moisture-stable Cu(I) and Ag(I) complexes, [Cu(NHC)Cl] and [Ag(NHC)Cl], in the recently discovered IPr^# family of ligands that hinge upon modular peralkylation of anilines. The complexes in both the BIAN and IPr families of ligands are reported. X-ray crystallographic analyses and computational studies were conducted to determine steric effects, Frontier molecular orbitals, and bond orders. The complexes were evaluated in the model hydroboration of the alkynes. We identified [Cu(BIAN-IPr^#)Cl] and [Ag(BIAN-IPr^#)Cl] as highly reactive catalysts with the reactivity outperforming the classical IPr and IPr*. Considering the attractive features of well-defined Cu(I)-NHC and Ag(I)-NHC complexes, this class of sterically bulky yet wingtip-flexible complexes will be of interest for catalytic processes in various areas of organic synthesis and catalysis.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11481170/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453476","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":"Alternate Geometries in the Cobalt-Catalyzed Hydroacylation of Dienes Facilitate a High Spin Mechanism: A Density Functional Theory Study","authors":"Thomas E. Shoopman,&nbsp;Andrew T. Morehead Jr.* and Andrew L. Sargent*,&nbsp;","doi":"10.1021/acs.organomet.4c0021510.1021/acs.organomet.4c00215","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00215https://doi.org/10.1021/acs.organomet.4c00215","url":null,"abstract":"<p >In contrast to the more common rhodium-catalyzed hydroacylation reaction, which is widely accepted to proceed via a low-spin singlet mechanism that passes through the familiar steps of oxidative addition → alkene insertion → reductive elimination, the cobalt-catalyzed hydroacylation reaction of dienes reported by Dong et al. ( <cite><i>J. Am. Chem. Soc.</i></cite>, <span>2014</span>) has been calculated to proceed via a high-spin triplet mechanism. The initial minimum energy pathway evaluated was the singlet, as two prior studies had also examined that pathway. The use of nudged elastic band methods enabled location of additional intermediates relative to the previous studies but also revealed that the isomeric product distribution was not accurately reproduced and that at least one intermediate appeared to prefer a different geometry. Subsequent examination of the triplet minimum energy pathway showed the intermediates are accompanied by geometries not typically associated with the singlet mechanism, which facilitates a very different pathway that involves oxidative cyclization and a direct reductive hydrogen atom transfer, thus avoiding the metal-hydride intermediates and reductive elimination steps that characterize the singlet pathway entirely.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142437566","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":"Alternate Geometries in the Cobalt-Catalyzed Hydroacylation of Dienes Facilitate a High Spin Mechanism: A Density Functional Theory Study","authors":"Thomas E. Shoopman, Andrew T. Morehead, Jr., Andrew L. Sargent","doi":"10.1021/acs.organomet.4c00215","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00215","url":null,"abstract":"In contrast to the more common rhodium-catalyzed hydroacylation reaction, which is widely accepted to proceed via a low-spin singlet mechanism that passes through the familiar steps of oxidative addition → alkene insertion → reductive elimination, the cobalt-catalyzed hydroacylation reaction of dienes reported by Dong et al. ( <cite><i>J. Am. Chem. Soc.</i></cite>, <span>2014</span>) has been calculated to proceed via a high-spin triplet mechanism. The initial minimum energy pathway evaluated was the singlet, as two prior studies had also examined that pathway. The use of nudged elastic band methods enabled location of additional intermediates relative to the previous studies but also revealed that the isomeric product distribution was not accurately reproduced and that at least one intermediate appeared to prefer a different geometry. Subsequent examination of the triplet minimum energy pathway showed the intermediates are accompanied by geometries not typically associated with the singlet mechanism, which facilitates a very different pathway that involves oxidative cyclization and a direct reductive hydrogen atom transfer, thus avoiding the metal-hydride intermediates and reductive elimination steps that characterize the singlet pathway entirely.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142254662","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":"Association and Aggregation of Magnesium Organocuprates","authors":"Sebastian Weske, Thomas Auth, Finn Kraft, Arne Winkler, Selina Schneider, Konrad Koszinowski","doi":"10.1021/acs.organomet.4c00233","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00233","url":null,"abstract":"Despite the frequent use of magnesium organocuprates derived from Grignard reagents in organic synthesis, the molecular composition of these important reagents is poorly understood. To achieve a better understanding of their speciation in solution, we apply here a combination of electrospray-ionization mass spectrometry, gas-phase fragmentation experiments, and quantum chemical calculations. For solutions of CuCl/2RMgCl (R = Ph, 2-thienyl, Bu, and Me₃SiCH₂) in tetrahydrofuran, we find anions of the type [Cu_<i>n</i>R_<i>n</i>+1]⁻, <i>n</i> = 1–6. Changing the copper precursor, increasing the amount of the Grignard reagent, and adding Me₂S have only relatively minor effects. Gas-phase fragmentation of the [Cu_<i>n</i>R_<i>n</i>+1]⁻ anions results in deaggregation reactions. In addition, [Cu_<i>n</i>Bu_<i>n</i>+1]⁻ and [Cu(CH₂SiMe₃)₂]⁻ undergo β-hydrogen and β-methyl eliminations, respectively, as well. Presumably, these decomposition pathways (as well as unknown processes) also occur in solution and explain the depletion of organyl substituents in the observed [Cu_<i>n</i>R_<i>n</i>+1]⁻ anions. The behavior of the magnesium cuprates deviates from that of the well-studied lithium cuprates, which display a higher tendency to form heteronuclear species. Our quantum chemical calculations for LiCuPh₂·LiCl and MgClCuPh₂·MgCl₂ in THF show that the absence of analogous heteronuclear complexes in the case of the magnesium cuprates results from higher relative Gibbs energies of these species.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142254664","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":"p-Aryl-Substituted Iminopyridine Chromium Complexes as Precatalysts for Ethylene Polymerization: The Question of the Physical Oxidation State Examined by Experimental and Density Functional Study in the Absence of Structural Data","authors":"Giorgia Zanchin, Alessia Amodio, Alessandro Piovano, Virginia Guiotto, Giuseppe Leone, Laura Falivene, Elena Groppo","doi":"10.1021/acs.organomet.4c00187","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00187","url":null,"abstract":"Investigations into iminopyridine chromium complexes have unveiled their potential as precatalysts for the polymerization of (di)olefins (<i>Organometallics</i> <b>2018</b>, <i>37</i>, 4827–4840). A Cr-to-ligand electron transfer, with the ligand (L) in the monoanionic radical state and Cr in a physical trivalent oxidation state, proved to be fundamental for facilitating ethylene polymerization by the complex with the unsubstituted aldimine (<b>Cr</b>-<i>p</i><b>H</b>, where X = H). In the absence of structural data, we embarked on a detailed study by ultraviolet–visible–near-infrared (UV–vis–NIR) spectroscopy and density functional theory to elucidate the structural and electronic features driving electron transfer in <b>Cr</b>-<i>p</i><b>H</b>. The Cr-to-L electron transfer is facilitated by the presence of two tetrahydrofurans in the metal’s coordination sphere in the monoligated form or by the formation of a bis-ligated species. The UV–vis–NIR spectra of <b>Cr</b>-<i>p</i><b>H</b>, coupled with electrospray ionization mass spectroscopy data, indicate the coexistence of multiple species. Successively, we enlarged the library of chromium complexes by appending different substituents (i.e., CH₃, OCH₃, and CF₃) at the <i>p</i>-<i>N</i>-aryl 4-position. While <b>Cr</b>-<i>p</i><b>CH</b>_<b>3</b> and <b>Cr</b>-<i>p</i><b>OCH</b>_<b>3</b> display electronic features analogous to those of <b>Cr</b>-<i>p</i><b>H</b>, <b>Cr</b>-<i>p</i><b>CF</b>_<b>3</b> stands out as an exception, likely containing only monoligated species. <b>Cr</b>-<i>p</i><b>CF</b>_<b>3</b> emerged as the most active catalyst, producing ultra-high-molecular weight poly(ethylene) with a unimodal and narrow molecular weight distribution event at 40 °C.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142254667","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: Rhodium Complexes of Acetamide-Derived PAlP Pincer","authors":"R. Noah Sladek, Nattamai Bhuvanesh, Oleg V. Ozerov","doi":"10.1021/acs.organomet.4c00351","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00351","url":null,"abstract":"The new alane/bis(phosphine) PAlP pincer-type ligands <b>2-Me</b> and <b>2-Et</b> have been prepared by protolysis reactions of <i>N</i>-(diisopropylphoshino)acetamide with Me₃Al or Et₃Al in a 2:1 ratio. Upon reaction with a “RhCl” source and pyridine, <b>2-Me</b> gave rise to a (PAlP)RhMe(py) compound (<b>4-Me</b>), while <b>2-Et</b> led to the analogous hydride complex (PAlP)RhH(py) (<b>4-H</b>), with a migration of the chloride from Rh to Al. <b>4-Me</b> and <b>4-H</b> possess the shortest Rh–Al bonds to date.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142254665","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":"p-Aryl-Substituted Iminopyridine Chromium Complexes as Precatalysts for Ethylene Polymerization: The Question of the Physical Oxidation State Examined by Experimental and Density Functional Study in the Absence of Structural Data","authors":"Giorgia Zanchin,&nbsp;Alessia Amodio,&nbsp;Alessandro Piovano,&nbsp;Virginia Guiotto,&nbsp;Giuseppe Leone*,&nbsp;Laura Falivene* and Elena Groppo*,&nbsp;","doi":"10.1021/acs.organomet.4c0018710.1021/acs.organomet.4c00187","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00187https://doi.org/10.1021/acs.organomet.4c00187","url":null,"abstract":"<p >Investigations into iminopyridine chromium complexes have unveiled their potential as precatalysts for the polymerization of (di)olefins (<i>Organometallics</i> <b>2018</b>, <i>37</i>, 4827–4840). A Cr-to-ligand electron transfer, with the ligand (L) in the monoanionic radical state and Cr in a physical trivalent oxidation state, proved to be fundamental for facilitating ethylene polymerization by the complex with the unsubstituted aldimine (<b>Cr</b>-<i>p</i><b>H</b>, where X = H). In the absence of structural data, we embarked on a detailed study by ultraviolet–visible–near-infrared (UV–vis–NIR) spectroscopy and density functional theory to elucidate the structural and electronic features driving electron transfer in <b>Cr</b>-<i>p</i><b>H</b>. The Cr-to-L electron transfer is facilitated by the presence of two tetrahydrofurans in the metal’s coordination sphere in the monoligated form or by the formation of a bis-ligated species. The UV–vis–NIR spectra of <b>Cr</b>-<i>p</i><b>H</b>, coupled with electrospray ionization mass spectroscopy data, indicate the coexistence of multiple species. Successively, we enlarged the library of chromium complexes by appending different substituents (i.e., CH₃, OCH₃, and CF₃) at the <i>p</i>-<i>N</i>-aryl 4-position. While <b>Cr</b>-<i>p</i><b>CH</b>_<b>3</b> and <b>Cr</b>-<i>p</i><b>OCH</b>_<b>3</b> display electronic features analogous to those of <b>Cr</b>-<i>p</i><b>H</b>, <b>Cr</b>-<i>p</i><b>CF</b>_<b>3</b> stands out as an exception, likely containing only monoligated species. <b>Cr</b>-<i>p</i><b>CF</b>_<b>3</b> emerged as the most active catalyst, producing ultra-high-molecular weight poly(ethylene) with a unimodal and narrow molecular weight distribution event at 40 °C.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142517796","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":"Fluorinated N-Heterocyclic Carbene Silver(I) Complexes with High Cancer Cell Selectivity","authors":"Oliver S. King,&nbsp;Benjamin J. Hofmann,&nbsp;Aran E. Boakye-Smith,&nbsp;Amy J. Managh,&nbsp;Tameryn Stringer and Rianne M. Lord*,&nbsp;","doi":"10.1021/acs.organomet.4c0029210.1021/acs.organomet.4c00292","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00292https://doi.org/10.1021/acs.organomet.4c00292","url":null,"abstract":"<p >This work presents the synthesis of five new functionalized (benz)imidazolium <i>N</i>-heterocyclic (NHC) ligands (<b>L</b>) and four new (benz)imidazole silver(I) NHC (Ag(I)-NHC) complexes of mononuclear <b>[Ag(L)₂](PF₆)</b> or binuclear <b>[Ag₂(L)₂](PF₆)₂</b> type. The complexes have been fully characterized, including single crystal X-ray diffraction of three new structures. The complexes and their corresponding free NHC ligands have been screened against breast cancer and noncancerous cell lines, showing the mononuclear benzimidazole complex has the highest activity, while the binuclear benzimidazole complex has the highest cancer cell selectivity. The silver uptake was measured by ICP-MS and highlights a strong link between cytotoxicity and cellular uptake. DNA interaction studies, molecular docking, and evaluation of reactive oxygen species (ROS) have been conducted for the most promising complexes to identify modes of action. Overall, the binuclear benzimidazole complex is the most selective and promising candidate against the MDA-MD-231 (breast cancer) cell line and has potential to be developed for treatment of late-stage breast cancers.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00292","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142517664","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":"Fluorinated N-Heterocyclic Carbene Silver(I) Complexes with High Cancer Cell Selectivity","authors":"Oliver S. King, Benjamin J. Hofmann, Aran E. Boakye-Smith, Amy J. Managh, Tameryn Stringer, Rianne M. Lord","doi":"10.1021/acs.organomet.4c00292","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00292","url":null,"abstract":"This work presents the synthesis of five new functionalized (benz)imidazolium <i>N</i>-heterocyclic (NHC) ligands (<b>L</b>) and four new (benz)imidazole silver(I) NHC (Ag(I)-NHC) complexes of mononuclear <b>[Ag(L)₂](PF₆)</b> or binuclear <b>[Ag₂(L)₂](PF₆)₂</b> type. The complexes have been fully characterized, including single crystal X-ray diffraction of three new structures. The complexes and their corresponding free NHC ligands have been screened against breast cancer and noncancerous cell lines, showing the mononuclear benzimidazole complex has the highest activity, while the binuclear benzimidazole complex has the highest cancer cell selectivity. The silver uptake was measured by ICP-MS and highlights a strong link between cytotoxicity and cellular uptake. DNA interaction studies, molecular docking, and evaluation of reactive oxygen species (ROS) have been conducted for the most promising complexes to identify modes of action. Overall, the binuclear benzimidazole complex is the most selective and promising candidate against the MDA-MD-231 (breast cancer) cell line and has potential to be developed for treatment of late-stage breast cancers.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142254669","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}