1996 Fiscal Year Final Research Report Summary
STRUCTURAL STUDY OF HYPERVALENT COMPOUNDS BY ^<121>Sb AND ^<127>I MossBAUER SPECTROSCOPY
| Project/Area Number |
06453053
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | TOHO UNIVERSITY |
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Principal Investigator |
TAKEDA Masuo TOHO UNIV., FAC.OF.SCI., PROFESSOR, 理学部, 教授 (80011633)
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| Co-Investigator(Kenkyū-buntansha) |
KITAZAWA Takafumi TOHO UNIV., FAC.OF.SCI., LECTURER, 理学部, 講師 (60246767)
TAKAHASHI Masashi TOHO UNIV., FAC.OF.SCI., ASSISTANT PROF., 理学部, 助教授 (30171523)
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| Project Period (FY) |
1994 – 1996
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| Keywords | Mossbauer spectroscopy / Hypervalent compounds / Structural Chemistry / Antimony / Iodine / Apical bonding / 3-center 4-electron bond |
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| Research Abstract |
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.
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Research Products
(4 results)
