CO_2 insertion into metal-carbon bonds: A computational study of Rh~I pincer complexes

Ostapowicz T.G.; H?lscher M.; Leitner W.

首页> 外文期刊>Chemistry: A European journal >CO_2 insertion into metal-carbon bonds: A computational study of Rh~I pincer complexes

【24h】

CO_2 insertion into metal-carbon bonds: A computational study of Rh~I pincer complexes

机译：CO_2插入金属-碳键中：Rh〜I夹合物的计算研究

获取原文

获取原文并翻译 | 示例

掌桥外文数据库（机构版） >>

开具论文收录证明 >>

文献代查 >>

页面导航

摘要
著录项
相似文献
相关主题

摘要

Catalytic carboxylation reactions that use CO_2 as a C1 building block are still among the 'dream reactions' of molecular catalysis. To obtain a deeper insight into the factors that control the fundamental steps of potential catalytic cycles, we performed a detailed computational study of the insertion reaction of CO_2 into rhodium-alkyl bonds. The minima and transition-state geometries for 38 pincer-type complexes were characterized and the according energies for the Ci-C bond-forming step were determined. The electronic properties of the Rhi-alkyl bond were found to be more important for the magnitude of the activation barrier than the interaction between rhodium and CO_2. The charge of the alkyl-chain carbon atom, as well as agostic and orbital interactions with the rhodium, exhibit the most pronounced influence on the energy of the transition states for the CO_2 insertion reaction. By varying the backbone and the donor groups of the pincer ligand those properties can be tuned over a very broad range. Thus, it is possible to match the electronic and steric properties with the fundamental requirements of the CO_2 insertion into rhodium-alkyl bonds of the ligand framework.

机译：使用CO_2作为C1结构单元的催化羧化反应仍然是分子催化的“梦想反应”。为了更深入地了解控制潜在催化循环基本步骤的因素，我们对CO_2插入铑-烷基键的插入反应进行了详细的计算研究。表征了38个钳型配合物的最小和过渡态几何构型，并确定了Ci-C键形成步骤的相应能量。发现Rhi-烷基键的电子性质对于活化势垒的大小比铑和CO_2之间的相互作用更重要。烷基链碳原子的电荷以及与铑的原子和轨道相互作用对CO_2插入反应的过渡态能量表现出最明显的影响。通过改变夹钳配体的主链和供体基团，可以在很宽的范围内调节这些性质。因此，可以使电子和位阻性质与将CO 2插入配体骨架的铑-烷基键中的基本要求相匹配。

著录项

来源
《Chemistry: A European journal》 |2011年第37期|共10页
作者
Ostapowicz T.G.; H?lscher M.; Leitner W.;
展开▼
作者单位

展开▼
收录信息
原文格式 PDF
正文语种 eng
中图分类
关键词
carbon dioxide; density functional calculations; insertion; pincer ligands; rhodium;

机译：二氧化碳密度泛函计算插入钳位配体铑;

相似文献

外文文献
中文文献
专利

1. CO_2 insertion into metal-carbon bonds: A computational study of Rh~I pincer complexes [J] . Ostapowicz T.G., H?lscher M., Leitner W. Chemistry: A European journal . 2011,第37期

机译：CO_2插入金属-碳键中：Rh〜I夹合物的计算研究
2. Reactivity of ortho-β-enaminone-phenyl palladium complexes. Insertion of CO into the Pd-C bond to give the first acyl C,N,O-pincer complexes. sequential insertion of dimethylacetylenedicarboxylate into the enaminone C-H bond and of isocyanide into the Pd-C Bond. A new photooxigenation/cyclization process [J] . Vicente J., Chicote M.T., Martínez-Martínez A.J., Organometallics . 2010,第21期

机译：邻-β-烯胺基-苯基钯配合物的反应性。将CO插入Pd-C键中，得到第一个酰基C，N，O-钳夹配合物。依次将二甲基乙酰二羧酸二甲酯插入到烯胺C-H键中，将异氰化物依次插入Pd-C键中。新的光氧合/环化过程
3. Computational studies of reactions of insertion of rhodium(I) and iridium(I) into N-H, N-CH_3, and NCH_2-H bonds of the diarylamine-based PNP pincer ligands [J] . Surawatanawong P., Ozerov O.V. Organometallics . 2011,第11期

机译：铑（I）和铱（I）插入基于二芳基胺的PNP钳型配体的N-H，N-CH_3和NCH_2-H键中的反应的计算研究
4. A Computational Study on the Insertion of N(~2D) into a C-H or C-C Bond: The Reactions of N(~2D) with Benzene and Toluene and Their Implications on the Chemistry of Titan [C] . Marzio Rosi, Leonardo Pacifici, Dimitrios Skouteris, International Conference on Computational Science and Its Applications . 2020

机译：将N（〜2D）插入C-H或C-C键的计算研究：N（〜2D）与苯和甲苯的反应及其对泰坦化学的影响
5. I. Synthesis, reactivity, and structural studies of rhodium(III) and rhodium(II) complexes of novel bis(oxazoline) pincer ligands. II. Synthesis and reactivity of novel rhenium methylidene complexes. [D] . Krumper, Jennifer. 2003

机译：I.新型双（恶唑啉）夹钳配体的铑（III）和铑（II）配合物的合成，反应性和结构研究。二。新型methyl亚甲基配合物的合成和反应性。
6. Experimental and computational study of alkane dehydrogenation catalyzed by a carbazolide-based rhodium PNP pincer complex [O] . David Bézier, Changjian Guan, Karsten Krogh-Jespersen, 2016

机译：咔唑基铑PNP钳夹配合物催化烷烃脱氢的实验与计算研究
7. Carbon-Oxygen Bond Formation at Metal(IV) Centers: Reactivity of Palladium(II) and Platinum(II) Complexes of the 2, 6-(Dimethylaminomethyl)phenyl-N, C, N- (Pincer) Ligand toward Iodomethane and Dibenzoyl Peroxide; Structural Studies of M(II) and M(IV) Complexes [O] . -1

机译：金属（IV）中心的碳 - 氧键形成：2,6-（二甲基氨基氨基甲基）苯基-N，C，N-（钳子）配体的钯（II）和铂（II）络合物的反应性朝向碘甲烷和二苯甲酰基的过氧化氢; M（II）和M（IV）复合物的结构研究
8. Activation Parameters for Rotation about a Metal-Carbon Bond from Temperature Dependent Proton N.m.r. Spectra of Rhodium Carbene Complexes. [R] . Doyle, M. J., Lappert, M. F. 1974

机译：从温度依赖的质子N.m.r.关于金属 - 碳键旋转的活化参数。铑卡宾配合物的光谱。

CO_2 insertion into metal-carbon bonds: A computational study of Rh~I pincer complexes

摘要

著录项

相似文献

相关主题

期刊订阅