由酸盐连接体支持的{Ni(NO) }10和{Co(NO) 2}10复合物的合成和表征
Andrew G Tennyson1, Shanta Dhar, Stephen J Lippard
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Journal of the American Chemical Society
|October 22, 2008
概括
研究人员探索了和硫酸盐复合物与氧化 (NO) 的反应,发现了新的阴离子复合物. 这项工作揭示了涉及NO和金属酶的生物过程中的潜在中间体.
科学领域:
- 无机化学 无机化学 有机化学
- 生物有机化学 生物有机化学
- 协调化学 协调化学
背景情况:
- 氧化 (NO) 是一个关键的生物信号分子,参与许多生理和病理生理过程.
- 的调节功能通常通过与铁,,和硫等氧化还原活性元素的相互作用来调节.
- 具有铁硫集群的金属酶与NO反应,形成dinitrosyl铁复合物,对小分子铁酸盐复合物的研究为这些反应提供了洞察力.
研究的目的:
- 从一个新的角度研究和硫酸盐复合物与氧化 (NO) 的化学成分.
- 为了确定铁硫酸盐化化合物的相互转化中的潜在中间体.
- 举报和复合体的第一个例子,其中包括{Ni(NO)}和{Co(NO) 2}单位.
主要方法:
- 新型和硫酸盐复合物的合成和表征.
- 研究这些复合物的与氧化 (NO) 和相关化合物的反应性.
- 利用质量平衡方法来发现新的复杂物.
主要成果:
- 报告了第一批含有{Ni(NO)} (10) 和{Co(NO) 2} (10) 单位的离子复合物.
- 合成了新型复合物,包括 (Et4N) 2[Ni(NO) ((SPh) 3), (Et4N) 2[Ni2 ((NO) 2 ((μ-SPh) 2 ((SPh) 2), (Et4N) [Co ((NO) 2 ((SPh) 2),和[Co3 ((NO) 6 ((μ-SPh) 3].
- 证明NO在某些复合物的合成中可以被Ph3CSNO取代.
结论:
- 新合成的和复合物的反应性表明,铁酸盐酸盐化合物的生物转化中可能存在中间体.
- 这项研究揭示了涉及NO和简单的酸盐支持和复合物的新化学成分.
- 这些发现扩大了我们对NO与金属有机化合物相互作用的理解.
相关概念视频
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.
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.
Coordination Compounds and Nomenclature
In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
Structure and Nomenclature of Thiols and Sulfides
Thiols and sulfides are sulfur analogs of alcohols and ethers, respectively, where the sulfur atom takes the place of the oxygen atom. Thus, thiols are generally represented as RSH, where R is an alkyl substituent and —SH is the functional group. On the other hand, in sulfides, the central sulfur atom is bonded to two hydrocarbon groups on either side. Depending upon the type of group, sulfides can be either symmetrical or asymmetrical. Both thiols and sulfides display a bent geometry, similar...
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...
Coordination Number and Geometry
For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.


