Organometallics最新文献_第3页

Rhodium-Catalyzed Arene Alkenylation: Selectivity and Reaction Mechanism as a Function of In Situ Oxidant Identity 铑催化的烯炔化反应：选择性和反应机理与原位氧化剂特性的关系

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-12 DOI: 10.1021/acs.organomet.4c00327

Marc T. Bennett, Kwanwoo A. Park, T. Brent Gunnoe

{"title":"Rhodium-Catalyzed Arene Alkenylation: Selectivity and Reaction Mechanism as a Function of In Situ Oxidant Identity","authors":"Marc T. Bennett, Kwanwoo A. Park, T. Brent Gunnoe","doi":"10.1021/acs.organomet.4c00327","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00327","url":null,"abstract":"Rhodium catalyzed arene alkenylation reactions with arenes and olefins using dioxygen as the direct oxidant (e.g., ACS Catal. 2020, 10, 11519), Cu(II) carboxylates (e.g., Science 2015, 348, 421; J. Am. Chem. Soc. 2017, 139, 5474) or Fe(III) carboxylate clusters (e.g., ACS Catal. 2024, 14, 10295), in the presence or absence of dioxygen, have been reported. These processes involve heating catalyst precursor [(η2-C2H4)2Rh(μ-OAc)]2, olefin, arene, and oxidant at temperatures between 120 and 200 °C. Herein, we report comparative studies of Rh-catalyzed arene alkenylation as a function of oxidant identity. This work includes comparisons of catalysis using Cu(II) carboxylates in the presence and absence of dioxygen, catalysis with only dioxygen as the oxidant, and Fe(III) carboxylates in the presence and absence of dioxygen. We report studies of catalysis with each oxidant including reagent concentration dependencies and kinetic isotope effect experiments using C6H6 or C6D6 and protio- or deutero carboxylic acid. Additionally, we probe ortho/meta/para regioselectivity for reactions of ethylene with monosubstituted arenes and Markovnikov/anti-Markovnikov selectivity with monosubstituted olefins. These studies indicate that the variation of oxidant identity impacts catalyst speciation, the reaction mechanism, and the reaction rate. Consequently, distinct Markovnikov/anti-Markovnikov and ortho/meta/para selectivities are observed for catalysis with each oxidant.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142180839","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-Complexed Acetylenic Tetrads, a Molecular Scaffold for Quadruple Ionic Functionalization Reactions 钴络合乙酰四烯，四重离子官能团化反应的分子支架

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-12 DOI: 10.1021/acs.organomet.4c0008810.1021/acs.organomet.4c00088

Gagik G. Melikyan*, Nicole Babayans, Natalie Kalpakyan, Claire Herrera, Pavel Rublev, Nikolay V. Tkachenko and Alexander I. Boldyrev*,

{"title":"Cobalt-Complexed Acetylenic Tetrads, a Molecular Scaffold for Quadruple Ionic Functionalization Reactions","authors":"Gagik G. Melikyan*, Nicole Babayans, Natalie Kalpakyan, Claire Herrera, Pavel Rublev, Nikolay V. Tkachenko and Alexander I. Boldyrev*, ","doi":"10.1021/acs.organomet.4c0008810.1021/acs.organomet.4c00088","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00088https://doi.org/10.1021/acs.organomet.4c00088","url":null,"abstract":"A methodology was developed for introducing nucleophiles into the α- and α′-positions of the dicobalt hexacarbonyl-complexed acetylenic tetrads. A synthetic algorithm included the entry of a given nucleophile to both termini of the acetylenic tetrad A (α-Nu1-α′-Nu1; α-Nu2-α′-Nu2), or a pair of select nucleophiles arranged unsymmetrically in opposing sequences (α-Nu1-α′-Nu2; α-Nu2-α′-Nu1). Thus, every substrate A and a pair of C-nucleophiles give rise to an organometallic rectangle (B-E) and synthetic octagon (B-I). The site-selective transformations that exploited the difference in thermodynamic stabilities of the α- and α′-cationoids, and thus in heterolytic bond dissociation energies (BDE) values, were coined the “quadruple ionic functionalization reactions.” The substrate and reagent bases were expanded to include aromatic carbo- and heterocycles as α-substituents, and aliphatic and aromatic reagents as nucleophiles. Density functional theory calculations allowed for identifying qualitative descriptors that explained the preponderant bond formation in more stabilized, albeit more hindered α-propargyl positions. In mechanistic terms, reactions at the competing sites (α- vs α-′) occupy distinctly different positions in the mechanistic continuum spanning the classical SN1 and SN2 processes. Overall, quadruple functionalization methodology allows for the practically limitless expansion of the acetylenic tetrads and a nucleophile base, and the completion of a multitude of organometallic rectangles and synthetic octagons.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276372","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: Ti-Catalyzed “Interrupted” Cascading Hydroamination of 1,6- and 1,7-En-ynes 闪电通讯：钛催化 1,6- 和 1,7- 烯炔的 "间断 "级联加氢反应

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-12 DOI: 10.1021/acs.organomet.4c0035410.1021/acs.organomet.4c00354

Kathryn J. Rynders, Daniel N. Huh, Zoe E. Stuart, Zoua Pa Vang and Ian A. Tonks*,

引用次数: 0

Mechanistic Insights into Rh-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic Silazanes: The Origin of Enantioselectivity 对 Rh 催化不对称合成硅烷的机理认识：不对称选择性的起源

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-11 DOI: 10.1021/acs.organomet.4c0026610.1021/acs.organomet.4c00266

Feiyun Jia*, Chenghua Zhang, Yongsheng Yang and Bo Zhang*,

{"title":"Mechanistic Insights into Rh-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic Silazanes: The Origin of Enantioselectivity","authors":"Feiyun Jia*, Chenghua Zhang, Yongsheng Yang and Bo Zhang*, ","doi":"10.1021/acs.organomet.4c0026610.1021/acs.organomet.4c00266","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00266https://doi.org/10.1021/acs.organomet.4c00266","url":null,"abstract":"The catalytic asymmetric synthesis of silazanes is always a challenging task. Here, a highly enantioselective synthesis of silicon-stereogenic silazanes was investigated to elucidate the protocol’s principal features and to clarify the origin of the enantioselectivity by using DFT calculations. The computational results indicate that the total free energy barrier for the conversion is 19.9 kcal/mol, which is reasonable given the current reaction conditions. Consistent with the experimental findings, the calculations indicate that σ-bond metathesis (N–H bond cleavage) is the rate-determining step for this transformation. Both pathways 1 and 2 toward S- or R-configuration products were investigated computationally. We found that the main enantiomer product of this transformation is determined by the kinetically more favorable main reaction pathway 1. Calculations indicate that the loss of one or the other H on the dihydrosilane will lock the product chirality; therefore, the oxidative addition is the enantioselectivity-determining step. Non-covalent interaction (NCI) analysis confirms that a difference in steric hindrance is responsible for the enantioselectivity of the protocol. Additionally, calculations confirm that the electron-donating group on aniline appropriately lowers the free energy barrier relative to the electron-withdrawing group (ΔG = 15.5 vs 21.6 kcal/mol), thereby accelerating the conversion.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276368","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

Mechanistic Insights into Rh-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic Silazanes: The Origin of Enantioselectivity 对 Rh 催化不对称合成硅烷的机理认识：不对称选择性的起源

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-11 DOI: 10.1021/acs.organomet.4c00266

Feiyun Jia, Chenghua Zhang, Yongsheng Yang, Bo Zhang

{"title":"Mechanistic Insights into Rh-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic Silazanes: The Origin of Enantioselectivity","authors":"Feiyun Jia, Chenghua Zhang, Yongsheng Yang, Bo Zhang","doi":"10.1021/acs.organomet.4c00266","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00266","url":null,"abstract":"The catalytic asymmetric synthesis of silazanes is always a challenging task. Here, a highly enantioselective synthesis of silicon-stereogenic silazanes was investigated to elucidate the protocol’s principal features and to clarify the origin of the enantioselectivity by using DFT calculations. The computational results indicate that the total free energy barrier for the conversion is 19.9 kcal/mol, which is reasonable given the current reaction conditions. Consistent with the experimental findings, the calculations indicate that σ-bond metathesis (N–H bond cleavage) is the rate-determining step for this transformation. Both pathways 1 and 2 toward S- or R-configuration products were investigated computationally. We found that the main enantiomer product of this transformation is determined by the kinetically more favorable main reaction pathway 1. Calculations indicate that the loss of one or the other H on the dihydrosilane will lock the product chirality; therefore, the oxidative addition is the enantioselectivity-determining step. Non-covalent interaction (NCI) analysis confirms that a difference in steric hindrance is responsible for the enantioselectivity of the protocol. Additionally, calculations confirm that the electron-donating group on aniline appropriately lowers the free energy barrier relative to the electron-withdrawing group (ΔG = 15.5 vs 21.6 kcal/mol), thereby accelerating the conversion.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142180836","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 of Cubic [Mo3S4M] (M = Rh, Ir) Clusters for the Borylation of C–H Bonds in Aromatic Compounds 用于芳香族化合物中 C-H 键硼化的立方 [Mo3S4M]（M = Rh、Ir）团簇的合成

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-11 DOI: 10.1021/acs.organomet.4c00283

Hitoshi Izu, Sayaka Shimoyama, Kazuki Tanifuji, Yasuhiro Ohki

{"title":"Synthesis of Cubic [Mo3S4M] (M = Rh, Ir) Clusters for the Borylation of C–H Bonds in Aromatic Compounds","authors":"Hitoshi Izu, Sayaka Shimoyama, Kazuki Tanifuji, Yasuhiro Ohki","doi":"10.1021/acs.organomet.4c00283","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00283","url":null,"abstract":"The incorporation of Rh or Ir into the [Mo3S4] platforms of [CpXL3Mo3S4] or [Cp*3Mo3S4] (CpXL = C5Me4SiEt3, Cp* = C5Me5) led to the formation of cubic [Mo3S4M] clusters, [CpXL3Mo3S4Rh(cod)] (1), [CpXL3Mo3S4Ir(coe)] (2), [Cp*3Mo3S4Rh(coe)] (3), and [Cp*3Mo3S4Ir(coe)] (4) (cod = 1,5-cyclooctadiene, coe = cyclooctene). These clusters were characterized spectroscopically and crystallographically. They catalyzed the C–H borylation of aromatic compounds (benzene, toluene, o-xylene, m-xylene, and p-xylene) in the presence of HBpin (4,4,5,5-tetramethyl-1,3,2-dioxaborolane), yielding the corresponding borylated products. Among these, cluster 3 exhibited the highest catalytic activity, while the treatment of cluster 2 with excess HBpin generated a millisecond-detectable potential intermediate, [CpXL3Mo3S4Ir(Bpin)]+. Despite the high affinity of Lewis acidic boron toward sulfur, the robust [Mo3S4M] (M = Rh, Ir) cubes protected adequately by Cp ligands have proven effective in borylation chemistry.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142180844","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

Investigating the Effects of Pulsed LED Irradiation in Photoredox Catalysis: A Pilot Study 调查脉冲发光二极管辐照在光氧化催化中的作用：试点研究

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-10 DOI: 10.1021/acs.organomet.4c00232

Liam K. Burt, Johnathon C. Robertson, Michael C. Breadmore, Timothy U. Connell, Alex C. Bissember

引用次数: 0

Flash Communication: A Ferrous Adduct of a Phosphanylidene-σ4-phosphorane 闪电通讯：亚磷酰σ4-磷烷的亚铁加合物

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-10 DOI: 10.1021/acs.organomet.4c00329

Ethan Zars, Matthew R. Mena, Michael R. Gau, Daniel J. Mindiola

{"title":"Flash Communication: A Ferrous Adduct of a Phosphanylidene-σ4-phosphorane","authors":"Ethan Zars, Matthew R. Mena, Michael R. Gau, Daniel J. Mindiola","doi":"10.1021/acs.organomet.4c00329","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00329","url":null,"abstract":"The sterically encumbered phosphanylidene-σ4-phosphorane Mes*PPMe3 (Mes* = 2,4,6-tBu3C6H2) smoothly displaces Et2O in [(tBupyrr2py)Fe(OEt2)] (1-OEt2) (tBupyrr2py2– = 3,5-tBu2-bis(pyrrolyl)pyridine) to form a rare example of a η1-phospha-Staudinger adduct of Fe, namely, [(tBupyrr2py)Fe(Mes*PPMe3)] (1-Mes*PPMe3) in 64% yield. Complex 1-Mes*PPMe3 is a ferrous, S = 2 system and quite thermally stable, but in the presence of B(C6F5)3 and photolysis, it forms the phosphaindan ferrous adduct [(tBupyrr2py)Fe(phosphaindan)] (1-phosphaindan) (phosphaindan = HPCH2C(Me2)-2,4-tBu2C6H2) along with Me3PB(C6F5)3. In the absence of Lewis acid, photolysis of 1-Mes*PPMe3 results instead in the formation of free phosphaindan and the PMe3 ferrous adduct [(tBupyrr2py)Fe(PMe3)] (1-PMe3) thus suggesting that dissociation of the phosphanylidene-σ4-phosphorane precedes the formation of a transient phosphinidene fragment Mes*P. All phosphorus adducts of 1 were crystallographically characterized and show quite similar Fe–P distances (2.4685(5) for 1-Mes*PPMe3; 2.5062(7) for 1-phosphaindan; and 2.4323(8) Å for 1-PMe3).","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142180841","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: A Ferrous Adduct of a Phosphanylidene-σ4-phosphorane 闪电通讯：亚磷酰σ4-磷烷的亚铁加合物

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-10 DOI: 10.1021/acs.organomet.4c0032910.1021/acs.organomet.4c00329

Ethan Zars, Matthew R. Mena, Michael R. Gau and Daniel J. Mindiola*,

{"title":"Flash Communication: A Ferrous Adduct of a Phosphanylidene-σ4-phosphorane","authors":"Ethan Zars, Matthew R. Mena, Michael R. Gau and Daniel J. Mindiola*, ","doi":"10.1021/acs.organomet.4c0032910.1021/acs.organomet.4c00329","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00329https://doi.org/10.1021/acs.organomet.4c00329","url":null,"abstract":"The sterically encumbered phosphanylidene-σ4-phosphorane Mes*PPMe3 (Mes* = 2,4,6-tBu3C6H2) smoothly displaces Et2O in [(tBupyrr2py)Fe(OEt2)] (1-OEt2) (tBupyrr2py2– = 3,5-tBu2-bis(pyrrolyl)pyridine) to form a rare example of a η1-phospha-Staudinger adduct of Fe, namely, [(tBupyrr2py)Fe(Mes*PPMe3)] (1-Mes*PPMe3) in 64% yield. Complex 1-Mes*PPMe3 is a ferrous, S = 2 system and quite thermally stable, but in the presence of B(C6F5)3 and photolysis, it forms the phosphaindan ferrous adduct [(tBupyrr2py)Fe(phosphaindan)] (1-phosphaindan) (phosphaindan = HPCH2C(Me2)-2,4-tBu2C6H2) along with Me3PB(C6F5)3. In the absence of Lewis acid, photolysis of 1-Mes*PPMe3 results instead in the formation of free phosphaindan and the PMe3 ferrous adduct [(tBupyrr2py)Fe(PMe3)] (1-PMe3) thus suggesting that dissociation of the phosphanylidene-σ4-phosphorane precedes the formation of a transient phosphinidene fragment Mes*P. All phosphorus adducts of 1 were crystallographically characterized and show quite similar Fe–P distances (2.4685(5) for 1-Mes*PPMe3; 2.5062(7) for 1-phosphaindan; and 2.4323(8) Å for 1-PMe3).","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276172","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-Rich Fused Clusters: Syntheses, Structures, and Bonding of Heteronuclear Condensed Metallaboranes 富金属融合簇：异核凝聚金属硼烷的合成、结构和结合

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-09 DOI: 10.1021/acs.organomet.4c0028810.1021/acs.organomet.4c00288

Shippy Jaiswal, Alaka Nanda Pradhan and Sundargopal Ghosh*,

{"title":"Metal-Rich Fused Clusters: Syntheses, Structures, and Bonding of Heteronuclear Condensed Metallaboranes","authors":"Shippy Jaiswal, Alaka Nanda Pradhan and Sundargopal Ghosh*, ","doi":"10.1021/acs.organomet.4c0028810.1021/acs.organomet.4c00288","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00288https://doi.org/10.1021/acs.organomet.4c00288","url":null,"abstract":"Syntheses and structural elucidations of a series of condensed clusters are described. The condensation of nido-[(Cp*Ru)2(B3H9)], nido-1, with heavier group 7 metal carbonyl, [Re2(CO)10], yielded [(Cp*Ru)2(CO)B3H8{Re(CO)3}], 2. Ruthenaborane 2 is an edge-fused cluster of square pyramid {RuReB3} and triangle {RuB2} through a B–B bond. Further, the reaction of arachno-[(Cp*Ru)2(B3H8)(CS2H)], arachno-3, with [Co2(CO)8] led to the formation of condensed ruthenaboranes [(Cp*Ru)2B3H3S{Co3(CO)8}(SCH3)], 4, and [(Cp*Ru)2B3H4{Co2(CO)7}(SCH3)], 5. Cluster 4 comprises two tetrahedron {Co2RuB}, {Co2BS} and pentagonal pyramidal {Co2RuB3} cores, and cluster 5 consists of a butterfly {Ru2B2}, a triangle {CoB2}, and a tetrahedron {Co2B2}. Both clusters 4 and 5 do not follow Mingos’ fusion formalism for fused clusters and are unusual examples based on their composition. On the other hand, cluster 2 follows Mingos’ fusion formalism. All of the clusters have been characterized by 1H, 11B{1H}, 13C{1H} NMR spectroscopies, electrospray ionization (ESI) mass spectrometry, and infrared (IR) spectroscopy, and the solid-state structures were established by single-crystal X-ray diffraction analysis.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276185","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