東京工業大学 · 材料科学
小坂田孝太郎教授の研究室は、遷移金属を用いた新しい有機金属触媒の開発に注力しており、特にニッケルやパラジウムを用いた高分子合成反応のメカニズム解明と触媒設計を柱としています。特にエチレンと機能性モノマーの共重合や、CO₂の不斉挿入反応、アルキンカップリング反応など、環境に配慮した合成手法の確立を目指しています。また、金属間距離や配位子の立体効果が反応選択性に与える影響を精密に制御する研究が特徴です。
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A dinuclear Ni complex with a double-decker structure (see scheme) and a short Ni–Ni distance promotes the copolymerization of ethylene with functional monomers. Matching of the Ni–Ni distance with the co-monomer structure resulted in polymers containing a high density of the co-monomer unit. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTNickel-Complex-Promoted Carboxylation of Haloarenes Involving Insertion of CO2 into NiII-C BondsKohtaro Osakada, Rei Sato, and Takakazu YamamotoCite this: Organometallics 1994, 13, 11, 4645–4647Publication Date (Print):November 1, 1994Publication History Published online1 May 2002Published inissue 1 November 1994https://pubs.acs.org/doi/10.1021/om00023a078https://doi.org/10.1021/om00023a078research-articleACS PublicationsRequest reuse permissionsArticl
The digold(I) complex [Au<sub>2</sub> Cl<sub>2</sub> (Cy<sub>2</sub> PCH<sub>2</sub> PCy<sub>2</sub> )] reacts with 4,4'-diphenylene diboronic acid to form a triangular macrocyclic complex with twisted Au-P-C-P-Au groups at the three corners. The synthesis of the complex and its chemical oxidation produced [6]cycloparaphenylene ([6]CPP) in 59 % overall yield.
trans-Pd(C6H4Me-p)(I)(PEt3)2 (2a) reacts with [Cu(C⋮CPh)(PPh3)]4 (Pd:Cu = 1:1) at room temperature to give the cross-coupling product PhC⋮CC6H4Me-p (3a) in 74% yield. Reactions of 2a with [Cu(C⋮CPh)(PPh3)]4 at −30 °C as well as of trans-Pd(C6H4X-p)(I)(PEt3)2 (2a, X = Me; 2b, X = OMe; 2c, X = F) with the alkynylcopper complex and additional PPh3 (2 mol/mol of Cu) at room temperature give mixtures of PhC⋮CC6H4X-p (3a, X = Me; 3b, X = OMe; 3c, X = F) and trans-Pd(C6H4X-p)(C⋮CPh)(PEt3)2 (4a, X = Me;
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPreparation, structure, and formation mechanism of ruthenium aryloxide complexes cis-RuH(OAr)(PMe3)4 (Ar = C6H5, C6H4-p-Me) and cis-RuH(OC6H4-p-CN)(PMe3)4(HOC6H4-p-CN)Kohtaro Osakada, Kimitaka Ohshiro, and Akio YamamotoCite this: Organometallics 1991, 10, 2, 404–410Publication Date (Print):February 1, 1991Publication History Published online1 May 2002Published inissue 1 February 1991https://pubs.acs.org/doi/10.1021/om00048a014https://doi.org/10.1021/om
Ethylene polymerization initiated by early-late transition-metal complexes afforded a polymer with different branched structures and properties depending on the type of late transition-metal.
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