Organometallics最新文献

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Formation of Homoleptic Zirconium and Hafnium Dithiocarbamates via Insertion of CS2: Breaking Bonds and Taking Names 通过插入 CS2 生成同色锆和铪二硫代氨基甲酸酯：断键和命名

IF 2.8 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics

Pub Date : 2024-06-19 DOI: 10.1021/acs.organomet.4c00152

Madeleine C. Uible, Brandon S. Prokop, Daniel C. Hayes, Subhajyoti Chaudhuri, Kiruba Catherine Vincent, Apurva A. Pradhan, Ace Rounds, Jonathan W. Turnley, Shubhanshu Agarwal, Ryan N. Swope, George C. Schatz, Rakesh Agrawal, Suzanne C. Bart

Syntheses of homoleptic zirconium and hafnium dithiocarbamates via carbon disulfide insertion into zirconium and hafnium amides were investigated for their utility as soluble molecular precursors for chalcogenide perovskites and binary metal sulfides. Treating M(NEtR)₄ (M = Zr, Hf and R = Me, Et) with CS₂ resulted in quantitative yields of homoleptic Group IV dithiocarbamates. Zr(κ²-S₂CNMeEt) (1), Zr(κ²-S₂CNEt₂)₄ (2), and Hf(κ²-S₂CNEt₂)₄ (4), a rare example of a crystal of a homoleptic hafnium CS₂-inserted amide species, were characterized. Computational analysis confirmed the assignments for IR spectroscopy. To exemplify the utility of the Group IV dithiocarbamates, a solution-phase nanoparticle synthesis was performed to obtain ZrS₃ via the thermal decomposition of Zr(S₂CNMeEt)₄.

研究人员通过二硫化碳插入锆和铪酰胺来合成同孔锆和铪二硫代氨基甲酸盐，以了解它们作为可溶性分子前驱体在铬化过磷酸盐和二元金属硫化物中的用途。用 CS2 处理 M(NEtR)4（M = Zr、Hf，R = Me、Et）可定量生成同色的第 IV 组二硫代氨基甲酸盐。对 Zr(κ2-S2CNMeEt) (1)、Zr(κ2-S2CNEt2)4 (2) 和 Hf(κ2-S2CNEt2)4 (4) 进行了表征。计算分析证实了红外光谱的分配。为了说明第 IV 族二硫代氨基甲酸酯的用途，我们进行了溶液相纳米粒子合成，通过 Zr(S2CNMeEt)4 的热分解获得了 ZrS3。

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引用次数: 0

Reactions of Titanium- and Zirconium-Based 1-Metallacyclobuta-2,3-diene Complexes with Diazenes: N═N Bond Cleavage versus N–C Bond Formation and Dearomatization 钛基和锆基 1-金属环丁-2,3-二烯配合物与二苯的反应：N═N 键裂解与 N-C 键形成和脱芳烃反应

IF 2.8 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics

Pub Date : 2024-06-18 DOI: 10.1021/acs.organomet.4c00142

Sihan Li, Mirjam Schröder, Xinzhe Shi, Anke Spannenberg, Jörg Fischer, Björn Corzilius, Fabian Reiß, Torsten Beweries

The reactions of two [rac-(ebthi)Ti]- and [rac-(ebi)Zr]-based 1-metallacyclobuta-2,3-diene complexes with diazenes are described. With azobenzene, cleavage of the N═N bond is observed in the case of Zr, leading to the formation of dinuclear Zr(IV) imido complex 1. In contrast, the insertion of azobenzene into the Ti–C bond of the titanacycle produces six-membered aza-metallacycle 6, which could only be characterized by nuclear magnetic resonance spectroscopy. With geometrically restricted benzo[c]cinnoline, activation and dearomatization of the phenyl group of the substrate occur, leading to the formation of unusual mononuclear [M = Zr (3)] and dinuclear complexes [M = Ti (7)]. Reaction mechanisms leading to the formation of these unusual complexes are proposed on the basis of control experiments.

本文描述了两种基于[rac-(ebthi)Ti]和[rac-(ebi)Zr]的 1-金属环丁-2,3-二烯配合物与二苯的反应。在偶氮苯中，观察到 Zr 的 N═N 键断裂，从而形成双核 Zr(IV) 亚氨基配合物 1。相反，将偶氮苯插入钛环的 Ti-C 键会产生六元杂氮金属环 6，只能通过核磁共振光谱来确定其特征。对于几何限制的苯并[c]噌啉，底物的苯基会发生活化和脱芳香化反应，从而形成不同寻常的单核[M = Zr (3)]和双核[M = Ti (7)]配合物。在对照实验的基础上，提出了形成这些不寻常络合物的反应机制。

引用次数: 0

Nickel-Catalyzed Hydrocarboxylation of Terminal Unactivated Alkenes: Formation of Branched Carboxylic Acids and Competing Catalyst Deactivation from CO2 Reduction to CO 镍催化末端未活化烯烃的加氢羧化反应：支链羧酸的形成和 CO2 还原成 CO 的催化剂竞争性失活

IF 2.8 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics

Pub Date : 2024-06-18 DOI: 10.1021/acs.organomet.4c00218

Fatemeh Khamespanah, James B. Gerken, David S. Mannel, Sandor Nagy, Barbara Kimmich, Shannon S. Stahl

The reductive coupling of CO₂ and alkenes represents a compelling strategy for the synthesis of carboxylic acids. In this study, we show that Ni(OAc)₂ and 6,6′-Me₂bpy (dmbpy) catalyze hydrocarboxylation of terminal unactivated alkenes to afford the branched 2-methyl-substituted carboxylic acids. The nickel/dmbpy speciation in solution is elucidated through electrochemical and UV–visible and NMR spectroscopic methods. A catalyst deactivation process is identified, involving competitive reduction of CO₂ to CO resulting in the formation of an inactive Ni–CO complex. The Ni catalyst may be reactivated by oxidative treatment of the Ni–CO complex to release CO; however, the results highlight an important complication that can arise in reactions of Ni-catalyzed reductive coupling with CO₂.

二氧化碳与烯烃的还原偶联是合成羧酸的一种有效策略。本研究表明，Ni(OAc)2 和 6,6′-Me2bpy（dmbpy）可催化末端未活化烯烃的羧化反应，生成支链 2-甲基取代羧酸。通过电化学、紫外-可见光和核磁共振光谱方法，阐明了溶液中镍/dmbpy 的规格。确定了催化剂失活过程，其中涉及 CO2 竞争性还原为 CO，形成无活性的 Ni-CO 复合物。镍催化剂可以通过氧化处理镍-CO 复合物来重新激活，从而释放出 CO；然而，研究结果突显了镍催化与 CO2 的还原偶联反应中可能出现的一个重要的复杂问题。

引用次数: 0

Photochemical Synthesis of Five-Membered Zirconacyclocumulene Complex and Its Reactions with Ketones 五元锆环茂林络合物的光化学合成及其与酮的反应

IF 2.8 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics

Pub Date : 2024-06-17 DOI: 10.1021/acs.organomet.4c00114

Mikhail A. Frolov, Maxim V. Andreev, Rinat R. Aysin, Vyacheslav S. Bogdanov, Alexander F. Smol’yakov, Vladimir V. Burlakov

Upon UV irradiation of zirconocene acetylides, five-membered zirconacyclocumulenes are formed. Subsequent photoexcitation or thermal activation of the mixture of tert-butyl-substituted complex with ketones leads to their mono- and/or diinsertion with the formation of zirconadihydrofuran and/or nine-membered dioxazirconacyclocumulene complexes, containing the [3]cumulene group in the ring. A combination of photochemical and thermal exposure enables sequential reactions of the tert-butyl-substituted complex with two different ketones.

紫外线照射锆烯乙酰化物后，会形成五元锆环茂烯类。随后，叔丁基取代络合物与酮的混合物经光激发或热活化后，会产生单插入和/或二插入反应，形成锆二氢呋喃和/或环内含有 [3]腙基的九元二噁锆环茂烯络合物。结合光化学和热暴露，可使叔丁基取代的络合物与两种不同的酮发生连续反应。

引用次数: 0

Highly Enantiomerically Enriched Secondary Alcohols via Epoxide Hydrogenolysis 通过环氧化物氢解实现高度对映体富集的仲醇

IF 2.8 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics

Pub Date : 2024-06-17 DOI: 10.1021/acs.organomet.4c00214

Olivia J. Borden, Benjamin T. Joseph, Marianna C. Head, Obsidian A. Ammons, Diane Eun Kim, Abigail C. Bonino, Jason M. Keith, Anthony R. Chianese

In this article, we report the development of ruthenium-catalyzed hydrogenolysis of epoxides to selectively give the branched (Markovnikov) alcohol products. In contrast to previously reported catalysts, the use of Milstein’s PNN-pincer-ruthenium complex at room temperature allows the conversion of enantiomerically enriched epoxides to secondary alcohols without racemization of the product. The catalyst is effective for a range of aryl epoxides, alkyl epoxides, and glycidyl ethers and is the first homogeneous system to selectively promote hydrogenolysis of glycidol to 1,2-propanediol, without loss of enantiomeric purity. A detailed mechanistic study was conducted, including experimental observations of catalyst speciation under catalytically relevant conditions, comprehensive kinetic characterization of the catalytic reaction, and computational analysis via density functional theory. Heterolytic hydrogen cleavage is mediated by the ruthenium center and exogenous alkoxide base. Epoxide ring opening occurs through an opposite-side attack of the ruthenium hydride on the less-hindered epoxide carbon, giving the branched alcohol product selectively.

在这篇文章中，我们报告了钌催化环氧化物氢解选择性生成支链（马可夫尼科夫）醇产物的研究进展。与之前报道的催化剂不同，在室温下使用米尔斯坦的 PNN-钳形钌络合物可以将对映体富集的环氧化物转化为仲醇，而不会使产物发生消旋化。该催化剂对一系列芳基环氧化物、烷基环氧化物和缩水甘油醚都有效，并且是首个能选择性地促进缩水甘油加氢分解为 1,2-丙二醇而不损失对映体纯度的均相体系。研究人员进行了详细的机理研究，包括在催化相关条件下对催化剂规格的实验观察、催化反应的全面动力学表征以及通过密度泛函理论进行的计算分析。异溶解氢的裂解是由钌中心和外源烷氧基碱介导的。环氧化物开环是通过钌氢化物对阻碍较少的环氧化物碳的反面攻击发生的，从而选择性地得到支链醇产物。

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引用次数: 0

Cobalt(I) Pincer Complexes as Catalysts for CO2 Hydrogenation to Formate 作为二氧化碳加氢生成甲酸盐催化剂的钳形钴（I）络合物

IF 2.8 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics

Pub Date : 2024-06-17 DOI: 10.1021/acs.organomet.4c00161

Wenzhi Yao, Gbolagade Olajide, Chance M. Boudreaux, Megan M. Wysocki, Md. Kausar Ahmed, Fengrui Qu, Tibor Szilvási, Elizabeth T. Papish

Carbon dioxide hydrogenation with a base to generate formate salts can provide a means of storing hydrogen in an energy-dense solid. However, this application requires catalytic CO₂ hydrogenation, which would ideally use an earth-abundant metal catalyst. In this article, six new (CNC)Co^IL₂ pincer complexes were synthesized and fully characterized including single-crystal X-ray diffraction analysis on four new complexes. These complexes contain an imidazole-based (1_R) N-heterocyclic carbene (NHC) ring or a benzimidazole-based NHC ring (2_R) in the CNC pincer. The R group is para to N on the pyridine ring and has been varied from electron-withdrawing (CF₃) to donating (Me, OMe) substituents. The L-type ligands have included CO and phosphine ligands (in ^PPh32 and ^PMe32). Thus, two known Co complexes (1, 1_OMe) and six new complexes (1_Me, 1_CF3, 2, 2_OMe, ^PPh32, and ^PMe32) were studied for the CO₂ hydrogenation reaction. In general, the unsubstituted CNC pincer complexes bearing two carbonyl ligands led to the highest activity. The best catalyst, 2, remains active for over 16 h and produces a turnover number of 39,800 with 20 bar of 1:1 CO₂/H₂ mixture at 60 °C. A computational study of the mechanism of CO₂ hydrogenation is also reported.

二氧化碳与碱氢化生成甲酸盐可以提供一种在高能固体中储存氢的方法。然而，这种应用需要催化二氧化碳氢化，最好使用富土金属催化剂。本文合成了六种新的 (CNC)CoIL2 钳子复合物，并对其进行了全面表征，包括对四种新复合物进行了单晶 X 射线衍射分析。这些复合物的 CNC 夹板中含有一个咪唑基 (1R) N-heterocyclic carbene (NHC) 环或一个苯并咪唑基 NHC 环 (2R)。R 基团是吡啶环上的对位 N 基团，其取代基可从吸电子（CF3）到供电子（Me、OMe）不等。L 型配体包括 CO 和膦配体（PPh32 和 PMe32）。因此，在二氧化碳加氢反应中研究了两种已知的 Co 配合物（1、1OMe）和六种新配合物（1Me、1CF3、2、2OMe、PPh32 和 PMe32）。一般来说，带有两个羰基配体的未取代 CNC 钳子配合物的活性最高。最佳催化剂 2 的活性可保持 16 小时以上，在 20 巴 1:1 CO2/H2 混合物（温度为 60 °C）条件下可产生 39,800 的周转次数。报告还对二氧化碳加氢的机理进行了计算研究。

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引用次数: 0

Synthesis of Methylated, Hydroxylated, and Aminated Metallaaromatics via Ring-Opening Reactions of the Fused Three-Membered Ring Units 通过融合三元环单元的开环反应合成甲基化、羟基化和胺化金属芳香族化合物

IF 2.8 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics

Pub Date : 2024-06-14 DOI: 10.1021/acs.organomet.4c00173

Jiawei Fei, Kexin Ma, Yonghong Ruan, Yapeng Cai, Yu-Mei Lin, Haiping Xia

引用次数: 0

Put a Ring on It: Improving the Thermal Stability of Molybdenum Imides through Ligand Rigidification 戴上戒指：通过配体刚性化提高钼酰亚胺的热稳定性

IF 2.8 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics

Pub Date : 2024-06-13 DOI: 10.1021/acs.organomet.4c00084

Michael A. Land, Kieran G. Lawford, Lara K. Watanabe, Marshall Atherton, Seán T. Barry

引用次数: 0

Dipyrromethene as a Ligand for the Stabilization of Low-Valent Gallium Complexes 作为配体稳定低价镓络合物的二吡咯并乙烯

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics

Pub Date : 2024-06-13 DOI: 10.1021/acs.organomet.4c00164

Tim Richter, Stefan Thum, Timothy Vilpas, Oliver P. E. Townrow, Lukas Klerner, Jens Langer and Sjoerd Harder*,

We investigated the low-valent chemistry of Al and Ga with the ligand ^tBuDPM, a dipyrromethene ligand scaffold with two large tBu groups in the flanking 1- and 9-positions and a mesityl group in the backbone 5-position. Attempted synthesis of (^tBuDPM)Al^I by reduction of (^tBuDPM)AlI₂ with KC₈ failed. However, reduction of (^tBuDPM)GaI₂ (1) with K/KI led to successful isolation of (^tBuDPM)Ga^I (3). The Ga^II intermediate in the reduction process crystallized as a digallane: [(^tBuDPM)GaI]₂ (2). Also, 3 crystallized as a dinuclear complex with a Ga–Ga bond. However, in a benzene solution, the 3 dissociates into two mononuclear complexes. Reaction of a benzene solution of (^tBuDPM)Ga^I with excess Me₃SiN₃ gave the tetrazagallole product (^tBuDPM)Ga[N₄(SiMe₃)₂] (4) and not the alternative azide-amide product (^tBuDPM)Ga(N₃)[N(SiMe₃)₂], which according to calculations is thermodynamically considerably more stable. Theoretical investigations on the nature of the Ga–Ga bonds in 2 and 3 and the mechanism for selective formation of 4 have been included.

我们研究了铝和镓与配体 tBuDPM 的低价化学反应。tBuDPM 是一种二吡咯烷配体支架，在侧翼 1 位和 9 位有两个大的 tBu 基团，在骨架 5 位有一个间苯二酚基团。用 KC8 还原 (tBuDPM)AlI2 合成 (tBuDPM)AlI 的尝试失败了。然而，用 K/KI 还原 (tBuDPM)GaI2 (1) 却成功地分离出了 (tBuDPM)GaI (3)。还原过程中的 GaII 中间体结晶为二镓烷：(tBuDPM)GaI]2 (2)。此外，3 结晶为具有 Ga-Ga 键的双核复合物。然而，在苯溶液中，3 会解离成两个单核络合物。(tBuDPM)GaI 的苯溶液与过量的 Me3SiN3 反应生成了四氮唑产物 (tBuDPM)Ga[N4(SiMe3)2] (4)，而不是另一种叠氮酰胺产物 (tBuDPM)Ga(N3)[N(SiMe3)2] ，根据计算，后者在热力学上要稳定得多。此外，还对 2 和 3 中 Ga-Ga 键的性质以及 4 的选择性形成机制进行了理论研究。

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引用次数: 0

Rhodium-Catalyzed Oxidative Alkenylation of Anisole: Control of Regioselectivity 铑催化的苯甲醚氧化烯基化反应：控制区域选择性

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics

Pub Date : 2024-06-13 DOI: 10.1021/acs.organomet.4c00155

Christopher W. Reid, and , T. Brent Gunnoe*,

We report the conversion of anisoles and olefins to alkenyl anisoles via a transition-metal-catalyzed arene C–H activation and olefin insertion mechanism. The catalyst precursor, [(η²-C₂H₄)₂Rh(μ-OAc)]₂, and the in situ oxidant Cu(OPiv)₂ (OPiv = pivalate) convert anisoles and olefins (ethylene or propylene) to alkenyl anisoles. When ethylene is used as the olefin, the o/m/p ratio varies between approximately 1:3:1 (selective for 3-methoxystyrene) and 1:5:10 (selective for 4-methoxystyrene). When propylene is the olefin, the o/m/p regioselectivity varies between approximately 1:8:20 and 1:8.5:5. The o/m/p ratios depend on the concentration of pivalic acid and olefin. For example, when using ethylene, at relatively high pivalic acid concentrations and low ethylene concentrations, the o/m/p regioselectivity is 1:3:1. Conversely, again for use of ethylene, at relatively low pivalic acid concentrations and high ethylene concentrations, the o/m/p regioselectivity is 1:5:10. Mechanistic studies of the conversion of anisoles and olefins to alkenyl anisoles provide evidence that the regioselectivity is likely under Curtin–Hammett conditions.

我们报告了通过过渡金属催化的炔烃 C-H 活化和烯烃插入机制将茴香醚和烯烃转化为烯基茴香醚的过程。催化剂前体[(η2-C2H4)2Rh(μ-OAc)]2 和原位氧化剂 Cu(OPiv)2（OPiv = 新戊酸酯）可将苯甲醚和烯烃（乙烯或丙烯）转化为烯基苯甲醚。当乙烯用作烯烃时，o/m/p 比率大约在 1:3:1 （对 3-甲氧基苯乙烯有选择性）和 1:5:10 （对 4-甲氧基苯乙烯有选择性）之间变化。当丙烯为烯烃时，o/m/p 的区域选择性大约在 1:8:20 和 1:8.5:5 之间变化。o/m/p 比率取决于新戊酸和烯烃的浓度。例如，在使用乙烯时，当新戊酸浓度相对较高而乙烯浓度较低时，o/m/p 区域选择性为 1:3:1。反之，同样是使用乙烯，当新戊酸浓度相对较低而乙烯浓度较高时，o/m/p 的选择性为 1:5:10。对苯甲醚和烯烃转化成烯基苯甲醚的机理研究证明，在柯廷-哈米特条件下可能会出现这种区域选择性。

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