Liquid-phase Dehydrogenation Catalysis for Alkane with Metal Cluster Complexes

金属簇配合物催化烷烃液相脱氢

• 批准号: 04453077
• 负责人: SAITO Yasukazu
• 金额: $ 5.12万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453077/
• 关键词: Alkane Dehydrogenation Catalyst; Ruthenium Cluster Complex; Platinum Cluster Complex; Catalyst Surface Modification with Cluster Complex; Carbonyl Ligand Dissociation; Diphosphine-bridged Complex; Rhodium Dinuclear Complex; Iridium Dinuclear Comple

A ruthenium carbonyl cluster complex Ru_3(CO)_<12> exhibited homogeneous catalysis for cyclooctane dehydrogenation, yielding cyclooctene and dihydrogen at T.O.N.= 69, whereas cyclohexanes were unreactive even under boiling and refluxing conditions in contrast to catalytically-active platinum or platinum-ruthenium composite fine particles.Pt-Ru composite catalysts were prepared from an ionic pair of Cs_2[Pt_3(CO)_6]_5 and [Ru(C_6Me_6)_2](BF_4)_2 by precepitation on a carbon support, followed by a heat treatment or from the surface modification of a platinum catalyst with a ruthenium hydrido-carbonyl complex H_4Ru_4(CO)_<12>. These composite catalysts were highly-active for dehydrogeno-aromatization of ethylcyclohexane.Photocatalytic alkane dehydrogenation was demonstrated with the A-frame dinuclear complexed of rhodium and iridium. It is noteworthy that the photoactive band at 365 nm of RhCl(CO)(PR_3)_2 is now extended to 475 nm (dinuclear Rh) and to 520 nm (dinuclear Ir), since it is important from the viewpoint of solar energy utilization.

钌羰基簇络合物Ru_3(CO)_<12>表现出对环辛烷脱氢的均相催化作用，在T.O.N.= 69时产生环辛烯和氢气，而与催化活性铂或铂-钌相比，环己烷即使在沸腾和回流条件下也不起反应。 由Cs_2[Pt_3(CO)_6]_5和[Ru(C_6Me_6)_2](BF_4)_2离子对在碳载体上沉淀、热处理或用钌氢化羰基络合物对铂催化剂进行表面修饰制备Pt-Ru复合催化剂 H_4Ru_4(CO)_<12>。这些复合催化剂对乙基环己烷脱氢芳构化反应具有很高的活性。以铑和铱的A型双核络合物证明了光催化烷烃脱氢。值得注意的是，RhCl(CO)(PR_3)_2 365 nm 处的光活性带现已扩展到 475 nm（双核 Rh）和 520 nm（双核 Ir），因为从太阳能利用的角度来看，这很重要。

项目成果

H.Itagaki,et al.: "Photocatalysis of RhCl(PCy_3)_2 for Cyclohexane Dehydrogenation:Thermal Dissociation of C-H Bond and Photoelimination of H_2" Bull.Chem.Soc.Jpn.67(in press). (1994)

H.Itagaki 等人：“RhCl(PCy_3)_2 用于环己烷脱氢的光催化：C-H 键的热解离和 H_2 的光消除”Bull.Chem.Soc.Jpn.67（印刷中）。

H.Itagaki, H.Einaga, Y.Saito: "Catalytic Cyclooctane Photodehydrogenation at Unusually Low Photon Energy with a Dinuclear Iridium Complex" Chem.Lett.2097-2098 (1993)

H.Itagaki、H.Einaga、Y.Saito：“使用双核铱配合物在异常低光子能量下催化环辛烷光脱氢”Chem.Lett.2097-2098 (1993)

M.Yamashita, N.Mou, Y.Sato, et al.: "New Energy Systems and Conversions" Universal Academy Press, Inc.4 (1993)

M.Yamashita、N.Mou、Y.Sato 等人：“新能源系统和转换”Universal Academy Press, Inc.4 (1993)

K.Yukawa,et al.: "Dehydrogeno-aromatization of Cyclohexanes with Suspended Noble-metal Catalysts" J.Chem.Soc.,Faraday Trans.89. 3641-3644 (1993)

K.Yukawa 等人：“用悬浮贵金属催化剂进行环己烷的脱氢芳构化”J.Chem.Soc.，Faraday Trans.89。

T.Fujii, Y.Higashino, Y.Saito: "Thermocatalytic Dehydrogenation of Alkanes with Wilkinson Complexes" J.Chem.Soc., Dalton Trans.517-520 (1993)

T.Fujii、Y.Higashino、Y.Saito：“烷烃与威尔金森配合物的热催化脱氢”J.Chem.Soc.，Dalton Trans.517-520 (1993)