STRUCTURAL STUDY OF HYPERVALENT COMPOUNDS BY ^<121>Sb AND ^<127>I MossBAUER SPECTROSCOPY

^<121>Sb 和 ^<127>I MossBAUER 光谱对高价化合物的结构研究

• 批准号: 06453053
• 负责人: TAKEDA Masuo
• 金额: $ 4.61万
• 依托单位: TOHO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06453053/
• 关键词: Mossbauer spectroscopy; Hypervalent compounds; Structural Chemistry; Antimony; Iodine; Apical bonding; 3-center 4-electron bond

Nature of the hypervalent bonds of X-Sb-X,O-Sb-X,O-Sb-O,N-Sb-X,C-Sb-X (X=halogens) and Cl-I-Cl, Cl-I-O,O-I-O in trigonal bipyramidal 10-Sb (V) -5, pseudo-trigonal bipyramidal 10-Sb (III) -4 with a lone pair, octahedral 12-Sb (V) -6 and pseudo-trigonal bipyramidal 10-I (III) -3 with two lone pairs was studied by ^<121>Sb and ^<127>I Mossbauer spectroscopy, and single crystal X-ray structural analysis.^<121>Sb and ^<127>I Mossbauer spectroscopy gave separately the information on the distribution of s- and p- electron density around Mossbauer atoms, thus the essential feature of the hypervalent bonds (3-center 4-electron bonds) as following was elucidated.(1) Both 5s and 5p_Z orbitals of antimony atoms being involved in the Sb-X bonding, it has both s and p character. On the other hand Sb-O bonding has mainly p character.(2) 5s orbitals of iodine do not contribute to l-O and l-Cl bond formation, only 5p_Z orbitals do.(3) The nature of the O-Sb-l bonding is very similar between trigonal bipyramidal 10-Sb (V) -5 and octahedral 12-Sb (V) -6.(4) The amount of negative charge on iodine depends on the strength of the Sb-l bondand the electronegativity of atom E in E-Sb-I (E=O,I,N,C) 3-c 4-e bond.

本文用穆斯堡尔谱和单晶X射线结构分析研究了三角双锥10-Sb（V）-5、假三角双锥10-Sb（III）-4、八面体12-Sb（V）-6和假三角双锥10-I（III）-3中X-Sb-X、O-Sb-X、O-Sb-O、N-Sb-X、C-Sb-X（X=卤素）和Cl-I-Cl、Cl-I-O、O-I-O超价键的性质<121><127>。<121>Sb穆斯堡尔谱和^<127>I穆斯堡尔谱分别给出了穆斯堡尔原子周围s-和p-电子密度分布的信息，从而阐明了超价键（3-中心4-电子键）的本质特征。(1)Sb原子的5s和5p_Z轨道都参与Sb-X键的形成，具有s和p两种性质。另一方面，Sb-O键主要具有p特征。(2)碘的5s轨道对l-O和l-Cl键的形成没有贡献，只有5p_Z轨道对l-O和l-Cl键的形成有贡献。(3)三角双锥10-Sb（V）-5和八面体12-Sb（V）-6之间的O-Sb-I键的性质非常相似。(4)碘上的负电荷量取决于Sb-1键的强度和E-Sb-I（E=O，I，N，C）3-c4-e键中E原子的电负性。

项目成果

M. Takahashi, M. Takeda et al: "^<127>I Mossbauer Spectra and X-ray Crytal Structures of Hypervalart Iodive(III)Complex of Hexafluorocumyl Alcohol and Related 10-I-3 Compounds" J. Coord, Chem.(in press). (1996)

M. Takahashi、M. Takeda 等人：“六氟异丙醇和相关 10-I-3 化合物的超价碘 (III) 络合物的^<127>I 穆斯堡尔谱和 X 射线晶体结构”J. Coord，Chem.(

M.Takahashi: "^<127>I Mossbauer Spectra and Xray Crystal Stncitures for Hypervalent Iodine (III) Conplex of Hex Luclomouyl Alcolnol and Related 10-I-3 Conpounds" J.Coord,Chem.37. 371-378 (1996)

M.Takahashi：“十六烷醇和相关 10-I-3 化合物的高价碘 (III) 复合物的 ^<127>I 穆斯堡尔谱和 X 射线晶体结构”J.Coord，Chem.37。

M.Takeda: "^<121>Sb Mossbauer spectra of Six-Coordinate Antimong (v) Complexes of Hexafluorocumyl Alcohol" Conf, Proc.-Ital.Phys.Stc., so (International Conference on the Applications of the Mossbauer Effect, 1995, Pt.2). 50. 107-110 (1996)

M.Takeda：“六配位 Antimong (v) 六氟枯醇复合物的^<121>Sb 穆斯堡尔谱”Conf，Proc.-Ital.Phys.Stc.，所以（穆斯堡尔效应应用国际会议，1995

M.Takeda: "^<121>Sb Mossbauer Spectra of Six-Coordinate Antinicny(V) Comploes of Hexafluorocamyl Alcohol" Conf. Proc. -Ital,Phys,Soc.,50(International Conference on the Applications of the Morsbauer Effectr 1995,Pt2). 50. 107-110 (1996)

M.Takeda：“六氟己醇六配位Annicny(V) Comploes的^<121>Sb Mossbauer光谱”Conf。

M,Takeda et al.: "^<121>Sb Mossbauer Spectra of Six-Coordinate Arctimony (V) Complexes of Hexafluorocumyl Alcohol" Conference Proceedings-Ital,Phys,Soc.,50 (International Conference on the Applications of the Mossbauer Effect,1995,Pt,2). 50. 107-110 (1996

M，Takeda 等人：“^<121>Sb Mossbauer Spectra of Six-Coordination Arctimony (V) Complexes of Hexa氟枯醇”会议论文集-Ital,Phys,Soc.,50（穆斯堡尔效应应用国际会议，