Development of Highly Efficient Bond Dissociation and Bond Formation Reactions Utilizing Group 6 Organometallic Complexes

利用第 6 族有机金属配合物开发高效键解离和键形成反应

• 批准号: 10450340
• 负责人: ITO Takashi
• 金额: $ 9.09万
• 依托单位: Yokohama National University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10450340/
• 关键词: group 6 transition metals; molybdenum; tungsten; bond-cleavage; bond-forming reaction; coordinative unsaturation; hydrido complexes; oxidative addition; モリブデンーケイ素結合; フェニルシラン; ゲルマン; 5座配位子; シクロペンタジエニル配位子; モリブデン-ケイ素結合; β-ジカルボニル化合物; シクロペンタジェニル配

Transition metal polyhydrido complexes are known to be potent precursors of the coordinatively unsaturated species because they often release dihydrogen via reductive elimination on light irradiation or heating in solution. In view of the highly reactive nature of the coordinatively unsaturated intermediate thus generated toward oxidative addition reactions, the research program utilizing [MH_4 (Ph_2PCH_2CH_2PPh_2)_2](1, M=Mo, W) and [MH_2 (η^5-C_5H_5)_2](2, M=Mo, W) as starting complexes for the selective bond cleavage and bond formation was undertaken. Complex 1 affords coordinatively unsaturated intermediate {MoH_2 (Ph_2PCH_2CH_2PPh_2)_2} and/or {Mo (Ph_2P-CH_2CH_2PPh_2)_2} on irradiation or heating in solution by releasing one or two moles of dihydrogen. The reactive intermediates thus formed were found to react with (1) methacrylic esters to cause olefinic C-H bond activation, (2) allyl carboxylates to give an η^2-carboxylato complex and propene as a result of C-O bond activation, (3) β-diketones and catechols to give chelated diketonato and catecholato derivatives, respectively, (4) cyclic imines and amides to cleave their N-H bonds to give N-acylamido complexes, or finally (5) aryl silanes or germanes to give a novel hydrido-silyl or-germyl complex which has a quinquedentate ligand comprising of a P〜P〜Si/Ge〜P〜P framework. The last complex was further investigated in view of the reactivity resulting from its unique structure. Complex 2 gives, on protonation with the acid such as p-toluene sulfonic acid, cationic trihydirdo complex, which exhibits selective reduction of organic functional group such as carbonyl and imine. The system was found also to reduce allylic alcohols to propane. Finally synthesis of the hitherto unknown carbene derivatives of molybdenocene was attempted and some new complex of such type were obtained.

过渡金属多金属络合物是配位不饱和物质的有效前体，因为它们在光照射或溶液中加热时经常通过还原消除释放出二氢。鉴于该配位不饱和中间体对氧化加成反应的高反应活性，我们以[MH_4（Ph_2PCH_2CH_2PPh_2）_2]（1，M=Mo，W）和[MH_2（η^5-C_5H_5）_2]（2，M=Mo，W）为起始配合物进行了选择性键断裂和键形成的研究。配合物1在溶液中照射或加热时释放1 ~ 2摩尔的氢，得到配位不饱和的中间体{MoH_2（Ph_2PCH_2CH_2PPh_2）_2}和/或{Mo（Ph_2 P-CH_2CH_2PPh_2）_2}。发现由此形成的反应性中间体与（1）甲基丙烯酸酯反应以引起烯属C-H键活化，（2）烯丙基羧酸酯反应以产生η^2-羧酸根络合物，并且由于C-O键活化而产生丙烯，（3）β-二酮和儿茶酚分别反应以产生螯合的二酮根和儿茶酚根衍生物，（4）环亚胺和酰胺裂解它们的N-H键得到N-酰氨基络合物，或最后（5）芳基硅烷或锗烷得到具有五齿配体的新的邻位甲硅烷基或邻位甲锗烷基络合物，所述配体包含P P Si/Ge P P骨架。最后一个配合物的反应性，从其独特的结构进行了进一步研究。配合物2与酸（如对甲苯磺酸）质子化生成阳离子三氢配合物，该配合物对羰基和亚胺等有机官能团具有选择性还原作用。该系统也被发现，以减少烯丙醇丙烷。最后尝试合成了一些新的茂碳烯衍生物，得到了一些新的茂碳烯配合物。

项目成果

D.-Y.Zhou: "Synthesis and Structural Characterization of the New Dioxygen Complexes of Molybdenum (IV)"Chemistry Letters. (2). 187-188 (1998)

D.-Y.Zhou：“钼（IV）新型双氧配合物的合成和结构表征”化学快报。

D.-Y.Zhou: "Novel concurrent Formation of Mo-Si and Si-C Bonds by the Reaction between [MoH_4(Ph_2PCH_2CH_2PPh_2)_2] and PhSiH_3" Chem.Lett.(10). 1017-1018 (1997)

D.-Y.Zhou：“通过[MoH_4(Ph_2PCH_2CH_2PPh_2)_2]和PhSiH_3之间的反应同时形成Mo-Si和Si-C键”Chem.Lett.(10)。

T.Ito: "Hydrido Complexes of Group 6 Transition Metals-Formation of the Quinquidentate Ligand Comprised of a P〜P〜Si〜P〜P Framework""Modern Coordination Chemistry : The Legacy of Joseph Chatt", the Royal Society of Chemistry. (to be published). (2001)

T.Ito：“第 6 族过渡金属的氢化配合物 - 由 P〜P〜Si〜P〜P 框架组成的五齿配体的形成”“现代配位化学：约瑟夫·查特的遗产”，英国皇家化学学会。 （待出版）。

M.Minato: "Methods of Molecular Transformations, Vol.2,2.7 Carbonyl Complexes of Cr.Mo. and W with σ-Bonded Ligands"Houben-Weyl Georg Thieme Verlag, Stuttgart,. (2001)

M.Minato：“分子转化方法，Vol.2,2.7 Cr.Mo. 和 W 与 σ-键合配体的羰基配合物”Houben-Weyl Georg Thieme Verlag，斯图加特，(2001)。

M.Minato: "Methods of Molecular Transformations, Vol.2, 2.7 Carbonyl Complexes of Cr, Mo, and W with σ-Bonded Ligands "Science of Syntheses""Houben-Weyl Georg Thieme Verlag, Stuttgart, (to be published). (2001)

M.Minato：“分子转化方法，第 2 卷，2.7 Cr、Mo 和 W 与 σ-键合配体的羰基配合物“合成科学””Houben-Weyl Georg Thieme Verlag，斯图加特，（待出版）。 (2001)