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- 田邊 真
- 東京工業大学資源化学研究所
書誌事項
- タイトル別名
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- Recent Researches on Activation and Dehydrocoupling of Amine-Boranes at Transition-Metal Centers
- センイ キンゾク サクタイ ニ ヨル アミンボラン ノ カッセイカ ト ダツスイソ ケツゴウ ケイセイ ニ カンスル サイキン ノ ケンキュウ
この論文をさがす
抄録
The catalytic dehydrocoupling reactions of amine-boranes have attracted considerable interest from the perspectives of chemical hydrogen storage and the production of new inorganic polymers. In this review, significant progress made in coordination of amine-boranes at transition metals is described, and the elementary reactions in relation to the catalyzed dehydrocoupling process are also discussed. Highly unsaturated complexes as the precursors provide an efficient strategy to synthesize the complexes with amine-borane ligands. The amine-borane s-complexes with the h1- or h2-coordination modes consist of electron-donation from the B-H bond to the metals exclusively and negligible back-donation to the B-H bond. The B-H activation (oxidative addition) of amine-boranes is achieved to the unsaturated Rh-PR3 system, giving unique dimeric complexes with Me3N-stabilized boryl ligands. The iridium amine-borane s-complexes convert thermally to the complexes with amino-borane ligands, together with elimination of hydrogen. X-ray crystallographic results of the ruthenium amino-borane s-complexes display shortening of the Ru-B and B-N bonds, indicating the B-N multiple-bond character. Dehydrocoupling reactions of primary and secondary amine-boranes promoted by a cationic iridium complex produce the linear diborazanes as kinetically stable products. The reaction pathway of the dehydrogenative oligomerization of amino-boranes is proposed.
収録刊行物
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- Bulletin of Japan Society of Coordination Chemistry
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Bulletin of Japan Society of Coordination Chemistry 60 (0), 34-37, 2012
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