Organometallics最新文献_第8页

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

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 2.8 3区化学

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

Shippy Jaiswal, Alaka Nanda Pradhan, Sundargopal Ghosh

{"title":"Metal-Rich Fused Clusters: Syntheses, Structures, and Bonding of Heteronuclear Condensed Metallaboranes","authors":"Shippy Jaiswal, Alaka Nanda Pradhan, Sundargopal Ghosh","doi":"10.1021/acs.organomet.4c00288","DOIUrl":"https://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":2.8,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142180843","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

Tuning the Electronic Properties of Azophosphines as Ligands and Their Application in Base-Free Transfer Hydrogenation Catalysis 调整偶氮膦配体的电子特性及其在无碱转移加氢催化中的应用

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-06 DOI: 10.1021/acs.organomet.4c00302

Emma J. Jordan, Ethan D. E. Calder, Bethan L. Greene, Holly V. Adcock, Louise Male, Paul W. Davies, Andrew R. Jupp

{"title":"Tuning the Electronic Properties of Azophosphines as Ligands and Their Application in Base-Free Transfer Hydrogenation Catalysis","authors":"Emma J. Jordan, Ethan D. E. Calder, Bethan L. Greene, Holly V. Adcock, Louise Male, Paul W. Davies, Andrew R. Jupp","doi":"10.1021/acs.organomet.4c00302","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00302","url":null,"abstract":"The design and tuning of new ligands is crucial for unlocking new reactivity at transition metal centers. Azophosphines have recently emerged as a new class of 1,3-P,N ligands in ruthenium piano-stool complexes. This work shows that the azophosphine synthesis can tolerate N-aryl substituents with strongly electron-donating and electron-withdrawing para-R groups and that the nature of this R group can affect the spectroscopic and structural properties of the azophosphines, as measured by NMR spectroscopy, UV–vis spectroscopy, single-crystal X-ray diffraction, and DFT studies. Azophosphines are shown to be relatively weak phosphine donors, as shown by analysis of the 1JP–Se coupling constants of the corresponding azophosphine selenides, but the donor properties can be fine tuned within this area of chemical space. Monodentate and bidentate Ru–azophosphine complexes were prepared, and their first use as a catalyst was probed. The Ru–azophosphine complexes were found to promote the transfer hydrogenation of acetophenone to 1-phenylethanol without the requirement of a harsh base additive, and the bidentate complex was more active than the monodentate analogue.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142180845","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

A Computational Study of Gold(I)-Catalyzed Isomerization of Cyclooctyne: A Case Study on the Mechanism of C(sp3)–H Insertion by Cationic Gold Alkyne Complexes and Model Studies 金（I）催化环辛炔异构化的计算研究：阳离子金炔离子配合物插入 C（sp3）-H 的机理案例研究和模型研究

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-06 DOI: 10.1021/acs.organomet.4c0035910.1021/acs.organomet.4c00359

Harrison E. Bruggeman, Rachel Lorson, Lilia J. Allen, Logan G. Jackson, Winston Gee and Brandon E. Haines*,

{"title":"A Computational Study of Gold(I)-Catalyzed Isomerization of Cyclooctyne: A Case Study on the Mechanism of C(sp3)–H Insertion by Cationic Gold Alkyne Complexes and Model Studies","authors":"Harrison E. Bruggeman, Rachel Lorson, Lilia J. Allen, Logan G. Jackson, Winston Gee and Brandon E. Haines*, ","doi":"10.1021/acs.organomet.4c0035910.1021/acs.organomet.4c00359","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00359https://doi.org/10.1021/acs.organomet.4c00359","url":null,"abstract":"Cationic gold-alkyne chemistry is a vital component of homogeneous gold catalysis due to its ability to access a wide range of reactive intermediates. Direct C(sp3)–H insertion by the cationic gold-alkyne complex is an emergent reaction in this area without a well-defined reactive intermediate. Gold(I)-catalyzed isomerization of cyclooctyne facilitated by trans-annular C(sp3)–H insertion ( <cite>Eur. J. Inorg. Chem.</cite> 2016, 995−1001) is used as a case study to investigate the mechanism of this process with density functional theory (DFT) calculations. Natural resonance theory (NRT) calculations are used to analyze the reactive intermediate in terms of familiar resonance structures. It is found that “slippage” or deformation of the gold ion coordination from η2 to η1 increases the NRT weighting of the vinyl cation resonance structure from 12% to 25% leading to its C(sp3)–H insertion reactivity. In addition, DFT calculations and a distortion-interaction analysis are used to rationalize the catalyst-dependent regioselectivity observed in the reaction. Lastly, model studies investigating the impact of the alkyne substrate and ancillary ligand show that electron-withdrawing substituents and electron deficient ligands lower Gibbs activation energy for C(sp3)–H insertion, which suggests strategies to further improve the reaction through catalyst design.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276404","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

Coordination Ability of Phosphavinyl(oxo and thioxo)phosphoranes (P═C–P═X; X = O, S) toward Transition Metals 磷酰基（氧代和硫代）磷烷（P═C-P═X；X = O、S）与过渡金属的配位能力

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-06 DOI: 10.1021/acs.organomet.4c00270

Iulia-Andreea Aghion, Raluca Septelean, Alex-Cristian Tomut, Ionut-Tudor Moraru, Albert Soran, Gabriela Nemes

{"title":"Coordination Ability of Phosphavinyl(oxo and thioxo)phosphoranes (P═C–P═X; X = O, S) toward Transition Metals","authors":"Iulia-Andreea Aghion, Raluca Septelean, Alex-Cristian Tomut, Ionut-Tudor Moraru, Albert Soran, Gabriela Nemes","doi":"10.1021/acs.organomet.4c00270","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00270","url":null,"abstract":"The coordination preferences of phosphavinylphosphorane species with the Mes*P═C(Cl)–PR1,R2(═X) general formula (Mes* = 2,4,6-trit-butylphenyl; X = O, S; R1 = Cl, R2 = 2,4,6-trii-propylphenyl; R1 = R2 = i-propyl) were evaluated in the presence of Au, W and Pd transition metals, by means of both experimental and theoretical investigations. Targeted compounds were characterized in solution by multinuclear NMR spectroscopy and HRMS, while for several cases, the solid-state structures were measured through X-ray diffraction. The preference for the coordination through the sulfur lone pair toward gold fragment was observed in the solid state, yet computational data highlight a possible fluxional character occurring in solution. Density functional theory mechanistic explorations suggest that the AuCl moiety shuttles between the P(III) and S atoms. Tungsten phosphavinylphosphorane complexes are stabilized by the phosphavinylphosphorane ligands in a bidentate coordination mode, involving both the P(III) and chalcogen atom. The coordination compounds with palladium fragments lead to the corresponding chelate compounds and the subsequent activation of a C–H bond from an ortho-methyl group of the Mes* group was observed if the P═C–P(═X) unit contained a Cl or O atom on the P(V) atom.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142180842","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