四个成员13组金属(I) N-异环碳类似物:合成,表征和理论研究
Cameron Jones1, Peter C Junk, Jamie A Platts
1School of Chemistry, Main Building, Cardiff University, Cardiff CF10 3AT, United Kingdom. jonesca6@cardiff.ac.uk
Journal of the American Chemical Society
|February 16, 2006
概括
研究人员合成了新的四个组成的13组金属 (I) heterocycles 和一个复合体. 理论研究表明,这些化合物作为有效的西格玛捐赠体配体起作用,扩大了协调化学的可能性.
科学领域:
- 无机化学 无机化学
- 有机金属化学 有机金属化学
- 协调化学 协调化学
背景情况:
- 与它们的金属 (III) 相比,13组金属 (I) 化合物的探索较少.
- 在现代化学中,N-异环碳 (NHCs) 是多功能联体.
- 对NHCs更重的13组类型的探索可以揭示独特的结合和反应性.
研究的目的:
- 合成和表征新型四个成员的13组金属 (I) 异环.
- 为了研究这些金属的结构和电子特性 (I) 复合物.
- 评估它们作为协调化学中的配体的潜力,与NHC进行并行.
主要方法:
- 合成具有特定N,N'-捐赠体连接体的单体Ga(I) 和In(I) 异环.
- 为进行比较研究而制备同位素复合物.
- 光谱技术 (NMR,IR等等) 是指光谱技术的使用. 和X射线晶体学用于结构阐明.
- 计算研究 (例如,DFT) 以了解电子结构和结合.
主要成果:
- 成功合成和分离了四个成员的Ga (I) 和In (I) 异环.
- 鉴定证实了金属中心周围的单体性质和特定的协调环境.
- 一个同质的复合物也被合成和研究.
- 理论计算表明,这些复合体表现出强大的西格玛捐赠能力.
结论:
- 已经成功地合成和特征化了新型四个成员的13组金属(I) 异环.
- 这些化合物是结构上类似于N-异环碳的化合物.
- 计算数据强烈支持它们在协调化学中作为有效的西格玛捐赠体连接体的潜力.
相关概念视频
Five-Membered Heterocyclic Aromatic Compounds: Overview
Heterocyclic aromatic compounds are cyclic compounds that are aromatic and have one or more heteroatoms—atoms other than carbon, in the ring. Depending upon the number of atoms present in the ring, they can be either five or six-membered. Examples of five-membered heterocyclic aromatic compounds include pyrrole, furan, thiophene, and imidazole. Pyrrole consists of one nitrogen atom having one lone pair of electrons. Furan and thiophene have one oxygen and one sulfur heteroatom, respectively.
Aromatic Hydrocarbon Cations: Structural Overview
Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group with both...
Removing one hydrogen from the intervening CH2 group with both...
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.
Frost Circles for Different Conjugated Systems
The inscribed polygon method is consistent with Hückel’s 4n + 2 rule and helps to learn whether the given cyclic compound is aromatic or not. The compound is stable and aromatic if every bonding molecular orbital (MO) is completely filled with a pair of electrons. However, if the non-bonding or antibonding orbitals are filled with electrons, the compound is unstable and not aromatic. Consider the Frost circle diagrams for cycloalkenes containing 4 to 8 carbons.
Structural Isomerism
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
Aromatic Hydrocarbon Anions: Structural Overview
Neutral hydrocarbons like cyclopentadiene with an odd number of carbon atoms and one intervening CH2 group in the ring are not aromatic. Cyclopentadiene with 4 π electrons does not satisfy the 4n + 2 π electron rule. Additionally, the intervening CH2 group is sp3 hybridized and lacks a vacant p orbital, thereby interrupting the overlap of p orbitals in a continuous manner and preventing the delocalization of π electrons throughout the ring.
Due to the absence of continuous overlap of p...
Due to the absence of continuous overlap of p...


