| Project/Area Number |
07404037
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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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 | HIROSHIMA UNIVERSITY |
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Principal Investigator |
MIYOSHI Katsuhiko Fac.Sci., HIROSHIMA UNIVERSITY Professor, 理学部, 教授 (60033924)
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| Co-Investigator(Kenkyū-buntansha) |
KUBO Kazuyuki Fac.Sci., HIROSHIMA UNIVERSITY Research Associate, 理学部, 助手 (90263665)
MIZUTA Tsutomu Fac.Sci, HIROSHIMA UNIVERSITY Research Associate, 理学部, 助手 (70221603)
NAKAZAWA Hiroshi Fac.Sci., HIROSHIMA UNIVERSITY Associate Professor, 理学部, 助教授 (00172297)
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| Project Period (FY) |
1995 – 1997
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| Project Status |
Completed (Fiscal Year 1997)
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| Budget Amount *help |
¥37,500,000 (Direct Cost: ¥37,500,000)
Fiscal Year 1997: ¥4,100,000 (Direct Cost: ¥4,100,000)
Fiscal Year 1996: ¥8,300,000 (Direct Cost: ¥8,300,000)
Fiscal Year 1995: ¥25,100,000 (Direct Cost: ¥25,100,000)
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| Keywords | Phosphenium Complex / Fe-P Double Bond / Stannylene Complex / Metallaphosphorane / Phosphamacrocycle Complex / Template / migratory insertion反応 / 金属フラグメントの転位 / ホスホラン錯体 / シクロペンタジエニルへの転位 / ホスファマクロサイクル / 金属-金属結合 / ホールサイズ / Migratory insertion反応 / X線構造解析 / ホスホネート錯体 / 転位反応機構 / Lewis酸 / 渡環相互作用 / 置換反応 |
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| Research Abstract |
(1) Study on Transition Metal-Phosphenium Complexes.
A new synthetic route to phosphenium complexes was developed treating with a Lewis acid a group 6 transition metal complex having a diamino-substituted phosphite as a ligand. A double bond character in the resulting P-M linkage was estimated on the basis of the reactivities, various spectroscopic data, substituent effect on the stability, and X-ray structures of the metal-phosphenium complexes thus obtained.
The corresponding complexes of iron (group 8) undergo similar but interesting reaction witha Lewis acid. That is, when the 14 group element ligand ER_3 coordinated to the iron atom is an alkyl group, it readily migrates to the phosphenium ligand, while such migration does not take place and the phosphenium complex is isolable when the ER_3 group is a silyl or germyl group. On the other hand, a stannylene complex is obtained for ER_3 being a stannyl group, where the alkyl group on the Sn atom but not the stannyl group itself migrates to the phosphenium ligand.
(2) Study on Phosphorane Complexes.
The iron complex having a triphenylphosphite is converted into the iron-phosphorane complex by the reaction with some Lewis bases, where the valency of the P atom is expanded to five. On the basis of its spectroscopic data and X-ray structures, it is claimed that the iron fragment acts as a pi-electron donor to the hhypervalent P atom. The pseudorotation characteristic of these compounds is also examined by variable temperature NMR.
(3) Study on Phosphamacrocycle Complexes.
Pd and Pt complexes with 14- and 16-membered phosphamacocyclic lignads were prepared by utilizing the template reaction. X-ray structures of these complexes revealed that the hole of the 14-membered phosphamacocyclic ligands is not sufficiently large to form less-constrained metal complexes.
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