边桥式Mo2Fe6S8到PN型Mo2Fe6S9集群转换:攻击硫化物/化物核的结构命运
Curtis P Berlinguette1, R H Holm
1Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
Journal of the American Chemical Society
|September 7, 2006
概括
合成了基酶P(N) 集群类似物. 这项研究揭示了这些铁硫团中独特的mu(6) -S原子的起源,澄清了核心转化途径.
科学领域:
- 生物有机化学 生物有机化学
- 协调化学 协调化学
- 材料科学 材料科学 材料科学
背景情况:
- 酶酶含有独特的P(N) 集群,对固化至关重要.
- 为了了解其结构-功能关系,P(N) 集群的合成类型是必不可少的.
- 在P(N) 集群类似物中,间歇性硫原子 (mu(6) -S) 的起源尚不清楚.
研究的目的:
- 合成和表征酶P(N) 集群的结构类型.
- 为了阐明反应机制和核心转换期间间歇性硫原子的起源.
- 为了研究核友在这些铁硫团的形成中的作用.
主要方法:
- 边缘桥接双立方集群的合成 [{Tp}{2}{M}{2}{6}{S}{8}{PEt}{3}{4}}} (1).
- 集群1与硫化 (SH-) 和化 (SeH-) 核的反应.
- 使用电喷式质谱学,1H NMR光谱学和X射线晶体学进行表征.
主要成果:
- 酶P (N) 集群的第一个结构类型的合成:[Tp (Tp) ]2M (M) 2Fe (Fe) 6S (S) 9SH (SH) 2S (S) 3S (S) 4S (M) =Mo,V).
- 识别间歇性mu(6) -S原子的起源来自前体,而不是攻击核爱好者.
- 化集群的制备[{Tp}{2}Mo{2}Fe{6}S{8}SeL{2}}{3}{-) 和二维集群,提供了对核心转化途径的见解.
结论:
- 攻击核爱好者可能会成为产品集群中的桥梁mu(2) -S原子.
- 3) -S和6) -S原子起源于起始边缘桥接的双古巴星团.
- 在这些P(N) 型集群的合成过程中,集群碎片化不太可能.
更多相关视频
07:14Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
04:51Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange
Published on: June 23, 2023
相关概念视频
Nuclear Transmutation
Nuclear transmutation is the conversion of one nuclide into another. It can occur by the radioactive decay of a nucleus, or the reaction of a nucleus with another particle. The first manmade nucleus was produced in Ernest Rutherford’s laboratory in 1919 by a transmutation reaction, the bombardment of one type of nuclei with other nuclei or with neutrons. Rutherford bombarded nitrogen-14 atoms with high-speed α particles from a natural radioactive isotope of radium and observed protons being...
Properties of Transition Metals
Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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.
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...
Valence Bond Theory
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
