Grant-in-Aid for Scientific Research on Priority Areas
|Allocation Type||Single-year Grants |
|Research Institution||OSAKA CITY UNIVERSITY |
OZAWA Fumiyuki Osaka City University, Professor, 工学部, 教授 (40134837)
MIYAURA Norio Hokkaido University, Professor, 大学院・工学研究科, 教授 (10002049)
TATSUMI Kazuyuki Nagoya University, Professor, 物資科学国際研究センター, 教授 (10155096)
SAKAKI Shigeyoshi Kumamoto University, Professor, 工学部, 教授 (20094013)
OSAKADA Kohtaro Tokyo Institute of Technology, 資源化学研究所, 教授 (00152455)
TOBITA Hiromi Tohoku University, Asso.Professor, 大学院・理学研究科, 助教授 (30180160)
|Project Period (FY)
1997 – 2000
Completed (Fiscal Year 2000)
|Budget Amount *help
¥89,500,000 (Direct Cost: ¥89,500,000)
Fiscal Year 1999: ¥30,500,000 (Direct Cost: ¥30,500,000)
Fiscal Year 1998: ¥30,000,000 (Direct Cost: ¥30,000,000)
Fiscal Year 1997: ¥29,000,000 (Direct Cost: ¥29,000,000)
|Keywords||Main group element-transition metal bond / Boron / Group 14 elements / Chalcogen atoms / Oxidative addition / Reductive elimination / Insertion / Transmetallation / ボウ素 / ケイ素 / ゲルマニウム / スズ / リン / イオウ / 遷移金属 / 錯体 / ジシリル錯体 / シリレン錯体 / ジボリル錯体 / スルフィド錯体 / 金属クラスター / ヒドロシリル化反応 / シリル錯体 / ゲルミル錯体 / ボリル錯体 / ジシリル化反応 / ジボリル化反応|
The following six subjects have been explored to establish new basic concepts for chemical bonding between main group elements and transition metals.
(1) Saturated Linkages between Main Group Elements and Transition Metals (F.Ozawa). A series of platinum (II) complexes bearing alkyl, silyl, germyl, and stannyl ligands have been prepared, and their structures and reactivities towards alkyne-insertion and reductive elimination have been examined by X-ray diffraction analysis, NMR spectroscopy, and kinetic experiments.
(2) Theoretical Study of the Reactions between Transition Metal Complexes and Inter-element Linkages (S.Sakaki). Oxidative addition of Si-B, Si-C, and Si-Si bonds towards a platinum (0) or palladium (0) complex has been examined by means of ab initio MO methods. The reactions of Si-C and Si-Si bonds proceed via an unusual non-planar transition state.
(3) Bonding and Reactions Characteristics of Early Transition Metal Chalcogenides (K.Tatsumi). A series of mononuclear, group 6
metal chalcogenides have been synthesized by the use of C-Y bond cleaving reactions. The resulting Cp^*MY_3 type complexes (Y=O, S, Se) serve as versatile building blocks of transition metal clusters.
(4) Transition Metal-catalyzed Reactions of Diborons (N.Miyaura). Transition-metal catalyzed activation of diboron compounds is an efficient way of synthesizing organoboron compounds which are versatile intermediates in organic synthesis. The reactions include diboration of unsaturated hydrocarbons, cross-coupling between diborons and organic halides, and conjugate addition of organoboronic acids to enones.
(5) Unsaturated Linkages between Main Elements and Transition Metals (H.Tobita). Base-stabilized silylene complexes have been prepared with a variety of late transition metals including rhodium, iridium, iron, and ruthenium, and a systematic study has been carried our for their structures and reactions. Some of the complexes undergo cycloaddition with C=O and C=N double bonds.
(6) Transmetallation of Thiolate and Silyl Ligands (K.Osakada). Mechanistic details of the title reaction have been gained by X-ray diffraction analysis of intermediates and reaction kinetics. A μ-silyl complex of dirhodium is a remarkable example. Less