| Project/Area Number |
01470052
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
無機・錯塩・放射化学
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| Research Institution | Heroshima University |
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Principal Investigator |
MIYOSHI Katsuhiko Hiroshima Univ., Dept. Chem., Professor, 理学部, 教授 (60033924)
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| Co-Investigator(Kenkyū-buntansha) |
MIZUTA Tsutomu Hiroshima Univ., Dept. Chem., Research Associate, 理学部, 助手 (70221603)
NAKAZAWA Hiroshi Hiroshima Univ., Dept. Chem., Associate Prof., 理学部, 助教授 (00172297)
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| Project Period (FY) |
1989 – 1990
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| Project Status |
Completed (Fiscal Year 1990)
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| Budget Amount *help |
¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1990: ¥400,000 (Direct Cost: ¥400,000)
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| Keywords | M=P double bond / Phosphonate complex / Phosphite complex / Arbuzov dealkylation / Metallaphosphorane / Migration reaction / Organometallics / Photo-chemical reaction / 遷移金属 / 二重結合 / アルブゾフ脱アルキル化 / アミノ置換ホスファイト / 光反応 / 転移反応 / 遷移金属リン二重結合 |
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| Research Abstract |
1. Preparation and Reactivity of Transition-metal Complexes Having a Multiple Bond to the Phosphorus
Treatment of Cr, Mo, and W complexes of various amino-substituted phosphites with BX_3 led to the formation of the cationic complexes with an M=P double bond, which are stabilized with increase in the amino-substitution and in chelation of the phosphite ligands and with the atomic number of the central metals.
2. Preparation of Transition-metal Phosphonate Complexes and the Mechanism
The Arbuzov-like dealkylation reaction of [Cp(CO)_2FeCl] with amino-substituted phosphites gave a cationic complex [Cp(CO)_2Fe[P(NR_2)Y(OR)]^+ (Y=OR,NR_2), which is regarded as an intermediate. The reaction of it with Cl^- yielded usual dealkylation products[Cp(CO)_2Fe[P(O)(NR_2)Y]], While the treatment with OR^- afforded a phosphonate complex [Cp(CO)_2Fe[P(0)Y(OR)]] where the NR_2 group is selectively eliminated. A plausible reaction mechanism is proposed in which a pentacoordinate metallaphosphorane is once formed with the NR_2 and incoming OR groups in axial positions, and then the OR group is attacked by another OR^- to release to release the NR_2^- group and the ether R_2O.
3. Migration of the Phosphonate Ligand from the Central to the Cp Ring
The phosphonate ligand P(0)RR' is found to migrate quantitatively to the Cp ring in [Cp(CO)LFe[P(O)RR']] when the complex is treated with LDA. The reaction mechanism was examined by use of some chiral phosphonate complexes.
4. Photo-chemical Reaction of Transition-metal Phosphonate Complexes
When the [Cp(CO)_2Fe[P(O)(OR)_2]] is irradiated with UV in the presence of L (L=PPh_3 or P(OR)_3), [Cp(CO)LFe[P(O)(OR)_2]] is formed with one CO group replaced by L, whereas a dimeric complex is formed in the absence of L, in which the P=0 group is coordinated in place of CO. The reaction was proved useful for synthetic purposes.
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