10组过渡金属的三化物复合物M (M = Pd, Pt)
Guohai Deng1, Yan Lu1, Tony Stüker1
1Department of Chemistry and Biochemistry, Freie Universität Berlin Fabeckstr. 34/36 14195 Berlin Germany ghdeng@zedat.fu-berlin.de s.riedel@fu-berlin.de.
Chemical science
|August 18, 2023
概括
和原子与三化物反应,形成M(NF3) 复合体. 这些复合物在蓝光照射后异构化为基化物FNMF2异构体,揭示了新的结合见解.
科学领域:
- 无机化学 无机化学
- 有机金属化学 有机金属化学
- 矩阵隔离光谱法 矩阵隔离光谱法
背景情况:
- 10组过渡金属如 (Pd) 和 (Pt) 是催化和材料科学中的关键.
- 三化 (NF3) 是一种具有独特电子特性的反应性化剂.
- 矩阵隔离技术允许在低温下研究过渡物种和反应机制.
研究的目的:
- 在惰性矩阵中研究Pd/Pt和NF3之间的反应.
- 描述最初的M(NF3) 复合体及其随后的异构化产物.
- 为了阐明这些新金属三化物相互作用中的电子结构和结合.
主要方法:
- 在冷温度下在固体虹和气矩阵中进行的反应.
- 使用红外吸收光谱学的M(NF3) 复合体和FNMF2异构体的形成和表征.
- 同位素替代研究 (例如,使用15N或19F) 来确认结构赋值.
- 理论频率计算和电子结构分析,以补充实验数据.
主要成果:
- 在Ne和Ar矩阵中,Pd和Pt原子成功地形成了N-协调的M(NF3) 复合体.
- 蓝色LED照射 (470nm) 通过迁移诱导M(NF3) 变异为更稳定的FNMF2异构体.
- 谱学和计算分析证实了具有双重结合的FN连接体的酸类物种的形成.
- 电子结构分析揭示了NF3的HOMO的显著sigma捐赠和金属d轨道的pi回捐赠,削弱了NF键.
结论:
- 这项研究证明了新型过渡金属-三化物复合物的形成和光诱导的异构化.
- 在M(NF3) 中的结合涉及到西格玛捐赠和pi回捐赠的组合,影响着连接体的稳定性.
- 由此产生的基化物 (FNMF2) 物种表现出 imido 特性,扩大了 NF3 与过渡金属的已知反应性.
相关概念视频
Exceptions to the Octet Rule
28.4K
Many covalent molecules have central atoms that do not have eight electrons in their Lewis structures. These molecules fall into three categories:
28.4K
Valence Bond Theory
8.7K
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...
8.7K
Coordination Number and Geometry
16.0K
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.
16.0K
Other Nuclides: 31P, 19F, 15N NMR
411
Many organic, inorganic, and biological molecules contain spin-half nuclei such as nitrogen-15, fluorine-19, and phosphorus-31. As a result, NMR studies of these nuclei have found extensive applications in chemical and biological research.
While fluorine-19 and phosphorous-31 have high natural abundances (100%) and positive gyromagnetic ratios, nitrogen-15 has a low natural abundance and a negative gyromagnetic ratio. However, nitrogen-15 is still preferred over nitrogen-14 (which has a...
While fluorine-19 and phosphorous-31 have high natural abundances (100%) and positive gyromagnetic ratios, nitrogen-15 has a low natural abundance and a negative gyromagnetic ratio. However, nitrogen-15 is still preferred over nitrogen-14 (which has a...
411
Coordination Compounds and Nomenclature
21.6K
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...
21.6K
Hybridization of Atomic Orbitals II
32.4K
sp3d and sp3d 2 Hybridization
32.4K


