![The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F54498.jpg&w=3840&q=50)
[Sn{9) Pt{2) }PPh{3) }{2) }-) と[Sn{9) Ni{2) }CO{3) }-) 複合体は,2つの明らかに異なるSn{9) M{2) L移行金属のジンチルイオン群とその動的行動である
Banu Kesanli1, James Fettinger, Donna R Gardner
1Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA.
Journal of the American Chemical Society
|April 25, 2002
まとめ
新しいチン・プラチナ・チン・ニッケル・クラスターが合成されました. これらの新しいクラスターは,溶液中の流動的行動と合成中のC-H活性化を含むユニークな構造と電子特性を有しています.
科学分野:
- 無機化学 無機化学とは
- 有機金属化学 有機金属化学
- マテリアルサイエンス 材料科学
背景:
- 亜鉛基クラスターは,独自の電子構造と潜在的な応用により興味を惹きます.
- 複雑なポリアニオンクラスターの合成には,しばしば特定の反応条件と安定剤が必要です.
研究 の 目的:
- 新種のチン・プラチナ・チン・ニッケル・クラスターを合成し,特徴づけること.
- これらの新しいクラスター化合物の構造的,電子的,動的性質を調査する.
- これらのクラスターの形成に関与する反応機構を探求する.
主な方法:
- アルカリ金属スタニド (K4Sn9) と移行金属前体 (Pt, Ni) を用いてチンのクラスターを合成する.
- X線 difraktion,NMRスペクトロスコピー (119Sn, 31P, 195Pt),EPRスペクトロスコピー,ESI-MS.を用いた特徴付けが行われました.
- デウテリウムラベル付けと水素化トラップ実験で,反応機構を研究する.
主要な成果:
- [Sn{9}Pt{2}PPh{3}]2- (2) の合成,溶媒のC−H活性化によって形成された,C3v対称性を持つ超閉じた10頂点のクラスタ.
- [Sn ((9) Ni ((2) ((CO)) ]3- (3) の合成は,C4v対称性を持つクローソ10頂点のクラスターであり,パラマグネティズムと超精密の相互作用を示しています.
- クラスター2は溶液中の流動的振る舞いを示し,固いPt-Pt-PPh3棒と一致する分子内交換があります.
- ESI-MSの分析により,両方のクラスターで親イオンと様々な関連種の形成が確認されました.
結論:
- 異なる構造および電子特性を有する新しい亜鉛移行金属クラスターが成功裏に合成されました.
- チン・プラチナ・クラスタの形成には,二重のC-H活性化経路が伴う.
- チン・プラチナ・クラスタの流動的振る舞いは,ポリイオニオン・クラスタのダイナミックなプロセスについての洞察を提供します.
関連する概念動画
02:37Metallic Solids
Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability. Many...
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability. Many...
02:57Coordination 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.
02:34Structural 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...
02:42Valence 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...
02:58Crystal Field Theory - Octahedral Complexes
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
03:02Colors and Magnetism
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.