Organometallics最新文献

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Diverted Telomerization Reaction with Aryl Boronic Derivatives: Expeditious Synthesis of Aryl-Substituted 1,6- and 1,7-dienes 芳基硼酸衍生物的转移端粒化反应:快速合成芳基取代的 1,6- 和 1,7- 二烯
IF 2.8 3区 化学
Organometallics Pub Date : 2024-07-10 DOI: 10.1021/acs.organomet.4c00203
Belén Lerma-Berlanga, José Pedro Cerón-Carrasco, Antonio Leyva-Pérez
{"title":"Diverted Telomerization Reaction with Aryl Boronic Derivatives: Expeditious Synthesis of Aryl-Substituted 1,6- and 1,7-dienes","authors":"Belén Lerma-Berlanga, José Pedro Cerón-Carrasco, Antonio Leyva-Pérez","doi":"10.1021/acs.organomet.4c00203","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00203","url":null,"abstract":"The telomerization reaction is a fundamental transformation in industry for the synthesis of highly substituted medium linear carbon chain products (8–12 carbon atoms) with heteroatoms (typically oxygen and nitrogen atoms). Here we show that this multibond forming reaction can be interrupted by adding an aryl boronic derivative in the reaction mixture, which diverts the reaction pathway from the final heteroatom toward the aryl coupling to give aryl-substituted 1,6- and 1,7-dienes in a very simple manner. Carbon chains between 14 and 30 carbon atoms can be prepared. Experimental and computational studies support a reaction mechanism that combines the classical telomerization reaction during the first steps and the Tsuji–Trost reaction for the last steps. These results open the way to designing different telomerization reactions where the final coupled fragment is not a canonical nucleophile.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141586720","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
Theoretical Studies on Relative Stability of Cationic 1,10-Phenanthroline Palladium Complexes Bearing Alkyl Groups by Using Designed Alkane Templates 利用设计的烷烃模板对含烷基的阳离子 1,10-菲罗啉钯配合物相对稳定性的理论研究
IF 2.8 3区 化学
Organometallics Pub Date : 2024-07-09 DOI: 10.1021/acs.organomet.4c00097
Kazuma Muto, Miho Hatanaka, Fumitoshi Kakiuchi, Takuya Kochi
{"title":"Theoretical Studies on Relative Stability of Cationic 1,10-Phenanthroline Palladium Complexes Bearing Alkyl Groups by Using Designed Alkane Templates","authors":"Kazuma Muto, Miho Hatanaka, Fumitoshi Kakiuchi, Takuya Kochi","doi":"10.1021/acs.organomet.4c00097","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00097","url":null,"abstract":"Density functional theory (DFT) calculations were conducted by using designed alkane templates, 2-methylpentane and 2-methylhexanes, which allowed for effective comparison of relative stabilities of alkylpalladium complexes with various numbers of branches at the α-carbon and the agostic β-carbon. The calculation results suggested that the alkylpalladium complexes bearing a 1,10-phenanthroline ligand are more stabilized when they have more branches at the α-carbon. In addition, the complexes with an agostic β-C(2°)–H or β-C(3°)–H bond generally have Gibbs free energies lower than those with an agostic β-C(1°)–H bond.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141586721","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
Diamidoamine Aluminum Complex as Effective Initiator for Random Copolymerization of Substituted Carbonate with L-Lactide 二氨基胺铝络合物作为取代碳酸酯与 L-内酯无规共聚的有效引发剂
IF 2.8 3区 化学
Organometallics Pub Date : 2024-07-09 DOI: 10.1021/acs.organomet.4c00078
Milana U. Agaeva, Vladislav I. Filippenko, Badma N. Mankaev, Valeriia A. Serova, Konstantin A. Lyssenko, Elena V. Chernikova, Mikhail P. Egorov, Sergey S. Karlov
{"title":"Diamidoamine Aluminum Complex as Effective Initiator for Random Copolymerization of Substituted Carbonate with L-Lactide","authors":"Milana U. Agaeva, Vladislav I. Filippenko, Badma N. Mankaev, Valeriia A. Serova, Konstantin A. Lyssenko, Elena V. Chernikova, Mikhail P. Egorov, Sergey S. Karlov","doi":"10.1021/acs.organomet.4c00078","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00078","url":null,"abstract":"Designing a catalyst for random copolymerization by ring-opening polymerization (ROP) is an actual task. In the present work, we report the synthesis of aluminum complexes (R′ = Et, R′′ = Ph (<b>5</b>); R′ = Bn, R′′ = Ph (<b>6</b>); R′ = <i>t</i>-Bu, R′′ = Ph (<b>7</b>); R′ = R′′ = Ph (<b>8</b>)] based on diamidoamine pro-ligands. The reactivity of complexes in the ROP of ε-caprolactone (ε-CL) was studied. The highest activity was shown by complexes <b>5</b> and <b>8</b>, containing phenyl groups at the terminal nitrogen atoms of the ligand in the ROP of ε-CL. Also, complex <b>5</b> was an effective initiator of copolymerization of 2-(benzyloxycarbonyl)-2-methyltrimethylene carbonate (TMC<sub>R</sub>) and <i>L</i>-lactide (<i>L</i>-LA) which led to the formation of a random copolymer.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141570234","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
Intrinsic Reactivity of [η5-1,3-(Me3C)2C5H3]2Th(bipy) toward Small Molecules η5-1,3-(Me3C)2C5H3]2Th(bipy)对小分子的内在反应性
IF 2.8 3区 化学
Organometallics Pub Date : 2024-07-05 DOI: 10.1021/acs.organomet.4c00149
Dongwei Wang, Yi Heng, Tongyu Li, Guofu Zi, Marc D. Walter
{"title":"Intrinsic Reactivity of [η5-1,3-(Me3C)2C5H3]2Th(bipy) toward Small Molecules","authors":"Dongwei Wang, Yi Heng, Tongyu Li, Guofu Zi, Marc D. Walter","doi":"10.1021/acs.organomet.4c00149","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00149","url":null,"abstract":"The reactivity of the thorium bipyridyl metallocene (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th(bipy) (<b>1</b>; Cp<sup>2<i>t</i>Bu</sup> = <i>η</i><sup>5</sup>-1,3-(Me<sub>3</sub>C)<sub>2</sub>C<sub>5</sub>H<sub>3</sub>) toward a series of small molecules was explored, and the emerging reactivity pattern can be categorized: (1) It may act as a synthon for (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th(II) in contact with alkynes, diazabutadienes, ketazine (Ph<sub>2</sub>C═N)<sub>2</sub>, <i>o</i>-benzoquinone, carbodiimides, organic azides, isothiocyanates, elemental sulfur (S<sub>8</sub>) and selenium (Se), and Ph<sub>2</sub>S<sub>2</sub>. (2) It participates in C–C coupling reactions with ketones Ph<sub>2</sub>CO, (CH<sub>2</sub>)<sub>5</sub>CO, and 1-indanone, aldehydes <i>p</i>-MePhCHO and <i>p</i>-ClPhCHO, amidate PhCONH(<i>p</i>-tolyl), seleno-ketone (<i>p</i>-MeOPh)<sub>2</sub>CSe, imines PhCH═NPh and (<i>p</i>-tolyl)<sub>2</sub>C═NH, ketazine (PhCH═N)<sub>2</sub>, and nitriles PhCN, Me<sub>3</sub>CCN, C<sub>6</sub>H<sub>11</sub>CN and CH<sub>3</sub>CN, to form (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(Ph<sub>2</sub>CO)] (<b>15</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)((CH<sub>2</sub>)<sub>5</sub>CO)] (<b>16</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(1-(C<sub>8</sub>H<sub>8</sub>)CO)] (<b>17</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(<i>p</i>-MePhCHO)] (<b>18</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(<i>p</i>-ClPhCHO)] (<b>19</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy){PhCONH(<i>p</i>-tolyl)}] (<b>20</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy){(<i>p</i>-MeOPh)<sub>2</sub>CSe}] (<b>21</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(PhCHNPh)] (<b>22</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy){(<i>p</i>-tolyl)<sub>2</sub>CNH}] (<b>23</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(PhCHNN═CHPh)] (<b>24</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(PhCN)] (<b>25</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(Me<sub>3</sub>CCN)] (<b>26</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(C<sub>6</sub>H<sub>11</sub>CN)] (<b>27</b>), and (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(CH<sub>3</sub>CN)] (<b>28</b>), respectively. However, in the presence of benzyl nitrile PhCH<sub>2</sub>CN, the dimeric bis-amido complex {(Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[NHC(CH<sub>2</sub>Ph)C(Ph)C(C(Ph)CN)NH]}<sub>2</sub> (<b>29</b>) is isolated. (3) Isonitriles such as Me<sub>3</sub>CNC, Me<sub>3</sub>SiNC, and C<sub>6</sub>H<sub>11</sub>NC undergo C–N bond cleavage and C–C coupling to furnish the thorium isocyanido amido complexes (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[4-(Me<sub>3</sub>C)bipy](NC) (<b>30</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[4-(Me<sub>3</sub>Si)bipy](NC) (<b>31</b>), and (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[4-(C<sub>6</sub>H<sub>11</sub>)bipy](NC) (<b>32</b>), respectively. A comparison with related thorium bipyridyl meta","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141570235","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
In Silico Discovery of a Neutral 2π Aromatic Silicon Aluminum Compound 中性 2π 芳香族硅铝化合物的硅学发现
IF 2.8 3区 化学
Organometallics Pub Date : 2024-07-04 DOI: 10.1021/acs.organomet.4c00151
Himanshu Sharma, Kumar Vanka
{"title":"In Silico Discovery of a Neutral 2π Aromatic Silicon Aluminum Compound","authors":"Himanshu Sharma, Kumar Vanka","doi":"10.1021/acs.organomet.4c00151","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00151","url":null,"abstract":"The recently developed <i>ab initio</i> nanoreactor (AINR) approach to identifying reaction intermediates and pathways without the necessity of experimental input has been employed in the current work to locate new cyclic silicon-based structures that have the potential to display aromaticity. Using this approach, we have identified many cyclic silicon-based molecules that have been experimentally reported over the past three decades. More importantly, the current work showcases an interesting new molecule that has been discovered through this approach: a four-membered cyclic compound of silicon and aluminum that displays significant 2π aromaticity and is capable of the activation of important small molecules such as ammonia.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141551340","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
Groups 9 and 10 Complexes of C–Donor Ligands Derived from Pyridinium-Stabilized Phosphorus Ylides 由吡啶稳定磷酰化物衍生的第 9 和第 10 组 C 供体配体
IF 2.8 3区 化学
Organometallics Pub Date : 2024-07-04 DOI: 10.1021/acs.organomet.4c00204
Anushree Poddar, F. Christopher Pigge
{"title":"Groups 9 and 10 Complexes of C–Donor Ligands Derived from Pyridinium-Stabilized Phosphorus Ylides","authors":"Anushree Poddar, F. Christopher Pigge","doi":"10.1021/acs.organomet.4c00204","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00204","url":null,"abstract":"The design and synthesis of η<sup>1</sup>-C-donor ligands that combine nucleophilic 4-alkylidene dihydropyridines with phosphorus ylides is reported. Positioning of a phosphonium group at the picolyl carbon of 4-alkylpyridinium salts allows for conversion to phosphonium-stabilized alkylidene dihydropyridine ligands under mildly basic conditions. The resulting (Me-N-Py-CH-PPh<sub>2</sub>-R)(BF<sub>4</sub>) ligands coordinate Pd(II)Cl<sub>2</sub> as monodentate (R = Ph) or bidentate ligands (R = 2-Py, CH<sub>2</sub>PPh<sub>2</sub>, or CH<sub>2</sub>CH<sub>2</sub>PPh<sub>2</sub>), and six new Pd(II) complexes were spectroscopically characterized. Structural features of four of the complexes were further defined through single-crystal X-ray diffractometry. The ligands in these complexes are best described as phosphorus ylide C-donors that are stabilized by adjacent <i>N</i>-methylpyridinium rings. In addition, two Rh(I) complexes were successfully prepared and characterized, including a Rh(I) carbonyl complex which exhibited a low ν<sub>CO</sub> of 1984 cm<sup>–1</sup>, indicative of the strong σ-donor properties of these ligands. The ability of a Pd complex to catalyze Suzuki cross-coupling reactions was examined.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141551338","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
Modulation of Phenolate-Functionalized Donor-Flexible PYE Ligands for Iridium-Catalyzed Formic Acid Dehydrogenation 用于铱催化甲酸脱氢反应的酚官能化捐献者柔性PYE配体的调制
IF 2.8 3区 化学
Organometallics Pub Date : 2024-07-03 DOI: 10.1021/acs.organomet.4c00116
Nicolas Lentz, Sabela Reuge, Alicia Beaufils, Martin Albrecht
{"title":"Modulation of Phenolate-Functionalized Donor-Flexible PYE Ligands for Iridium-Catalyzed Formic Acid Dehydrogenation","authors":"Nicolas Lentz, Sabela Reuge, Alicia Beaufils, Martin Albrecht","doi":"10.1021/acs.organomet.4c00116","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00116","url":null,"abstract":"Formic acid (FA) is a promising hydrogen carrier. Recently, we developed a formally underligated iridium(III) complex [Ir(Cp*)(O,N)]<sup>+</sup> (Cp* = pentamethylcyclopentadienyl, C<sub>5</sub>Me<sub>5</sub><sup>–</sup>; O,N = pyridylidene amine (PYE)-phenolate) <b>1a</b> as a high performing catalyst for FA dehydrogenation. Here, we exploited the facile synthetic accessibility of the PYE-phenolate ligand to investigate the influence of the ligand on FA dehydrogenation. Comparison of the activity of <b>1a</b> with related iridium complexes containing ligands derived either from hydroxy-quinoline or <i>N</i>-aryl-aminophenol (complexes <b>2</b> and <b>3</b>) indicate that neither a static imine nor a static anionic amide bonding of the nitrogen site induces catalytic activity, in contrast to the donor-flexible PYE nitrogen in <b>1a</b>. Introduction of substituents on the phenolate donor (−OMe, −Me, −H, −Cl, and −NO<sub>2</sub>, complexes <b>4</b>–<b>7</b>), and on the PYE heterocycle (−Me, −H, and −Cl, complexes <b>8</b>–<b>10</b>), as well as comparison of the <i>ortho-</i>PYE with its <i>meta-</i> and <i>para-</i>isomers (complexes <b>11</b>–<b>13</b>) indicate a narrow window of electronic and steric tolerance before catalytic activity decreases. Evaluation of electron density at the iridium center via cyclic voltammetry (CV) as well as chemical shift and half-life time of the iridium-hydride intermediate derived from complexes <b>4</b>–<b>7</b> reveals a direct correlation between iridium electron density, hydride stability, and Hammett σ<sub>p</sub> parameters, though not with the catalytic activity of these complexes. This work indicates therefore that catalytic activity is not governed by maximizing hydricity or iridium electron density but by optimizing these parameters.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141551339","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
Compounds with Chelating 3-Dimethylamino-1-propyl Ligands as Chemical Vapor Deposition Precursors. Synthesis and Characterization of M[(CH2)3NMe2]2 Complexes of Nickel(II), Palladium(II), and Platinum(II) 作为化学气相沉积前驱体的 3-二甲基氨基-1-丙基螯合配体化合物。镍(II)、钯(II)和铂(II)的 M[(CH2)3NMe2]2配合物的合成与表征
IF 2.8 3区 化学
Organometallics Pub Date : 2024-07-02 DOI: 10.1021/acs.organomet.4c00186
R. Joseph Lastowski, Vincent J. Flores, Laurent Souqui, John R. Abelson, Gregory S. Girolami
{"title":"Compounds with Chelating 3-Dimethylamino-1-propyl Ligands as Chemical Vapor Deposition Precursors. Synthesis and Characterization of M[(CH2)3NMe2]2 Complexes of Nickel(II), Palladium(II), and Platinum(II)","authors":"R. Joseph Lastowski, Vincent J. Flores, Laurent Souqui, John R. Abelson, Gregory S. Girolami","doi":"10.1021/acs.organomet.4c00186","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00186","url":null,"abstract":"We describe the synthesis and characterization of three new square-planar compounds of stoichiometry M[(CH<sub>2</sub>)<sub>3</sub>NMe<sub>2</sub>]<sub>2</sub>, where M = Ni, Pd, or Pt, each of which contains two chelating 3-dimethylamino-1-propyl ligands. The nickel(II) and palladium(II) compounds decompose above −78 and 0 °C, respectively, but the platinum(II) compound has a thermolysis onset temperature of 130 °C. The Pd and Pt complexes are dynamic in solution: they undergo ring inversion with small free energies of activation of Δ<i>G</i><sup>⧧</sup> = 7.9 ± 0.1 and 8.3 ± 0.1 kcal mol<sup>–1</sup>, respectively, at 298 K. The Pt complex sublimes at 40 °C and 5 mTorr. In benzene solution, the Pt compound thermolyzes primarily through β-hydrogen elimination; 80 ± 10% of the hydrogen atoms and 75 ± 5% of the carbon atoms from the precursor can be accounted for in the byproducts. The thermolysis of the Pt complex in C<sub>6</sub>D<sub>6</sub> follows first-order kinetics, with an activation free energy Δ<i>G</i><sup>⧧</sup> of 29.9 ± 0.1 kcal mol<sup>–1</sup> at 110 °C. Under CVD conditions, thin films grown of the Pt complex at 200 °C contain nanocrystalline Pt; analysis of the film growth byproducts suggest that the main decomposition pathway involves β-hydrogen elimination and reductive elimination steps, as seen in solution.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141506920","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
Molecular Rigidification of Cyclometalated N∧C∧N Pt(II)- and Pd(II)-Based Triplet Emitters 环甲基化 N∧C∧N 铂(II)和钯(II)基三重发射极的分子刚性化
IF 2.8 3区 化学
Organometallics Pub Date : 2024-07-01 DOI: 10.1021/acs.organomet.4c00121
Maryam Niazi, Iván Maisuls, Cristian A. Strassert, Axel Klein
{"title":"Molecular Rigidification of Cyclometalated N∧C∧N Pt(II)- and Pd(II)-Based Triplet Emitters","authors":"Maryam Niazi, Iván Maisuls, Cristian A. Strassert, Axel Klein","doi":"10.1021/acs.organomet.4c00121","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00121","url":null,"abstract":"In an effort to develop transition metal complexes with efficient phosphorescence, we synthesized cyclometalated complexes [M(N<sup>∧</sup>C<sup>∧</sup>N)Cl] (M = Pd or Pt) with amine groups NH(C<sub>6</sub>H<sub>5</sub>) at the two <i>ortho</i>-positions of the pyridyl rings (HL<sup>NHPh</sup>) or NH(C<sub>6</sub>H<sub>5</sub>CH<sub>2</sub>) (HL<sup>NHBn</sup>) for intramolecular hydrogen bonding with the Cl<sup>–</sup> coligand. Single-crystal X-ray diffractometry confirmed the hydrogen bonding and showed a distorted square planar geometry around the metal centers with τ<sub>4</sub> values of around 0.25 due to marked distortion of the Cl<sup>–</sup> coligand from the coordination plane. Long-wavelength UV–vis absorption energies are increased for Pt vs Pd. The Pt(II) complexes are intense triplet emitters in solution at 298 K (λ<sub>max</sub> = 520 nm) and at 77 K. The Pd(II) derivatives showed vibrationally structured phosphorescence bands in a frozen glassy matrix at 77 K resembling those of the Pt complexes but were nonemissive in liquid solutions at 298 K. The DFT-optimized electronic structures of the complexes show comparable geometries in their singlet ground state (<i>S</i><sub>0</sub>) and in the first triplet (<i>T</i><sub>1</sub>) excited states. Both are distorted by a combination of steric repulsion of the bulky <i>ortho</i>-RNH groups of the tridentate N<sup>∧</sup>C<sup>∧</sup>N ligands, the Cl<sup>–</sup> coligand, and the N–H···Cl···H–N hydrogen bonds.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141506921","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
Six-Membered Iridacycles with Five Nitrogen Atoms in the Ring 环中含有五个氮原子的六元铱环
IF 2.8 3区 化学
Organometallics Pub Date : 2024-07-01 DOI: 10.1021/acs.organomet.4c00163
J. Drake Johnson, Andrew J. King, Fu-Sheng Wang, Aleksandr V. Zhukhovitskiy
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