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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
奥斯-三重键:奥斯-复合物的合成,表征和反应性
Paul G Hayes1, Zhenggang Xu, Chad Beddie
1Department of Chemistry, University of California, Berkeley, Berkeley, California 94720-1460, USA.
Journal of the American Chemical Society
|August 3, 2013
概括
研究人员合成了第一个用超出6组的金属合成的烯复合物,该金属具有独特的三重键. 这一突破使得能够观察到与终端基因的新型循环添加反应.
科学领域:
- 有机金属化学 有机金属化学
- 化学 化学
- 协调化学 协调化学
背景情况:
- 具有-联体三重键特征的烯复合物很少见,特别是在6组以外的金属中.
- 了解这些复合物的结合和反应性对于推进无机和有机金属化学至关重要.
研究的目的:
- 合成和描述第一个含有6组以外的金属的烯复合物.
- 为了阐明金属-键的性质,并研究基连接体的反应性.
主要方法:
- 通过从中提取化物来合成烯复合物.
- 使用核磁共振 (NMR) 光谱学进行表征.
- 计算分析包括密度函数理论 (DFT),自然键轨道 (NBO) 和用化学价值自然轨道进行能量分解分析 (ETS-NOCV).
主要成果:
- 成功制备了第一个米金属的西利林复合物,[Cp*((i) Pr3P) ((H) OsSi ((Trip) ]][HB(C6F5) 3].
- 核磁共振和DFT研究证实了西利因配体,并揭示了由西格玛键和两个pi回捐特征的三重键.
- 观察了第一个涉及西里林复合物的循环添加反应,特别是通过与终端基因的OsSi键的C-H键添加.
结论:
- 该研究报告说,通过将其扩展到6组以外的金属,烯化学取得了重大进展.
- Os-Si 三重键表现出强烈的共价性和原始性结合相互作用.
- 烯复合体所表现出的新型反应性为合成转化开辟了新的途径.
相关概念视频
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
Preparation and Reactions of Sulfides
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
Properties of Organometallic Compounds
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
Resonance
The Lewis structure of a nitrite anion (NO2−) may actually be drawn in two different ways, distinguished by the locations of the N-O and N=O bonds.
Preparation and Reactions of Thiols
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
Lewis Structures of Molecular Compounds and Polyatomic Ions
To draw Lewis structures for complicated molecules and molecular ions, it is helpful to follow a step-by-step procedure as outlined:

