Facile Activation of Protic Molecules by Ir (I) and Rh (I) Complexes and Their Application

Ir(I)和Rh(I)配合物对质子分子的简易活化及其应用

• 批准号: 10650850
• 负责人: YAMAGATA Tsuneaki
• 金额: $ 1.54万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650850/
• 关键词: dinuclear iridium complex; catalytic transfer hydrogenation; X-ray structure analysis; asymmetric hydrogenation; catalytic hydration; oxidative addition; imine; alkyne; 二核イリジウム錯体; 酸化的付加

I have found that dinuclear IrィイD1IィエD1 complexes [IrCl(diphosphane)]ィイD22ィエD2 carrying even perarylphospanes which are not so strong electron donting {diphosphane=2,2'-bis(diphenylphosphino)-1,1'-binapthyl (BINAP) or bis(diphenylphosphino)-1,1'-biphenyl(BPBP)} can easily activate protic molecules {MeOH, HィイD22ィエD2O, RCOィイD22ィエD2H(R=Me, Ph), PhSH} at ambient temperature. The concrete structure of [{Ir{(R)-binap}(H)(μ-OMe)}ィイD22ィエD2(μ-Cl)] Cl.MeOH has confirmed by X-ray analysis, spectaral data, and elemental analysis. The reactions of [IrCl(diphophane)]ィイD22ィエD2 and protic molecules{HィイD22ィエD2O, RCOィイD22ィエD2H(R=Me, Ph), PhSH} gave hydrido(hydroxo)-, hydrido(carboxylato)-, and hydido(thilato)-complexes, respectively. Those complexes are also considered to takeanalogous dinuclear structures by NMR spectal data, elemental analyses, and limiting equivalent conductances. The complex [IrCl(diphosphane)]ィイD22ィエD2 easily reacted with two equivalents of neutral ligands{PPhィイD23ィエD2, PCyィイD23ィエD2, P(OPh)ィイD23ィエD2}at ambient temperature to give the corresponding mononuclear complexes in good yield. I have found that the mononuclear complexes react with molecular hydrogen or methanol to give the dihydrido-iridium complex IrCl(H)ィイD22ィエD2(diphosphane)(L)(L=PPhィイD23ィエD2, PCyィイD23ィエD2).I have found that hydrido(methoxo) complexes serve as efficient catalyst precursors for reduction of internal alkynes to give trans-alkenes using methanol as a source of hydrogen. Overhydrogenation to alkanes was also accompanied.The hydrido(carboxylato)-iridium(III) complex was found to be active for asymmetric hydrogenation of prochiral imines in toluene or toluene/MeOH to optically active amines.The hydrido(hydroxo)-iridium(III) complex was found to be active for hydration of nitriles (acetonitrile or benzonitrile). I am examining the optimization of catalytic hydration.

我发现双核Ir D1 I D1配合物[IrCl（二膦）]双膦D2, 2双膦D2，其甚至带有不那么强的电子给予的全芳基膦{二膦= 2，2 '-双（二苯基膦基）-1，1 '-联萘（BINAP）或双（二苯基膦基）-1，1 '-联苯（BPBP）}在环境温度下可以容易地活化质子分子{MeOH，H_CN_D22_CN_D2 O，RCO_CN_D22_CN_D2 H（R=Me，Ph），PhSH}。[{Ir{（R）-binap}（H）（μ-OMe）}双氯D22双氯D2（μ-Cl）] Cl·MeOH的具体结构经X射线分析、光谱数据和元素分析证实。[IrCl（diphophane）]双氯D22双氯D22与质子分子{H双氯D22双氯D2 O，RCO双氯D22双氯D2 H（R=Me，Ph），PhSH}反应，分别得到双（羟基）-、双（羧基）-和双（噻吩基）-配合物。这些配合物也被认为是takeanalogous双核结构的NMR光谱数据，元素分析，和限制等效电导。配合物[IrCl（diphosphane）]双膦D22双膦D2与2当量的中性配体{PPh双膦D23双膦D2，PCy双膦D23双膦D2，P（OPh）双膦D23双膦D2}在室温下反应，得到相应的单核配合物。我发现单核配合物与分子氢或甲醇反应生成二氢铱配合物IrCl（H）-D22-D22（diphosphane）（L）（L=PPh-D23-D22，PCy-D23-D22）。我发现二氢铱（甲氧基）配合物是用甲醇作为氢源还原内炔生成反式烯烃的有效催化剂前体。在甲苯或甲苯/甲醇体系中，铱（Ⅲ）配合物对前手性亚胺的不对称氢化反应具有催化活性，而铱（Ⅲ）配合物对腈（乙腈或苄腈）的水合反应具有催化活性.我在研究催化水合的最优化。

项目成果

Kazuhide Tani, Tsuneaki Yamagata, Yasutaka Kataoka, and Kazushi Mashima: "Activation of E-H (E=heterom atom) and C-H bonds by Iridium Complexes and Their Application to Homogeneous Catalysis."Yuki gosei kagaku kyoukaishi. 57 (8). 656-666 (1999)

Kazuhide Tani、Tsuneaki Yamagata、Yasutaka Kataoka 和 Kazushi Mashima：“铱配合物对 E-H（E=杂原子）和 C-H 键的活化及其在均相催化中的应用。”Yuki gosei kagaku kyoukaishi。

谷一英: "Facile Oxidative Addition of O-H Bonds of Methanol and Water to Ir^I Complexes Having Peraryldiphosphine Ligands ; Isolation and Characterization of Hydrido(methoxo)-and Hydrido(hydroxo) complexes of Ir^<III>"Angew. Chem. Int. Ed.. 37. 3381-3383 (19

Kazuhide Tani：“甲醇和水的 O-H 键与具有过芳基二膦配体的 Ir^I 配合物的轻松氧化加成；Ir^<III> 氢化（甲氧基）-和氢化（羟基）配合物的分离和表征”Angew Int. .. 37. 3381-3383 (19

谷一英: "Efficient transfer hydrogeneration of alkynes and alkenes with methanol catalysed by Hydrido(methoxo)iridium(III) complexes"Chem. Commun.. 1821-1822 (1999)

Kazuhide Tani：“Hydrido(methoxo)irid(III) 配合物催化的甲醇和炔烃的高效转移氢化”Chem. 1821-1822 (1999)

Kazuhide Tani, Aika Iseki und Tsuneaki Yamagata.: "Leichte oxidative Addition von Methanol und Wasser an Peraryldiphosphan-IrィイD1IィエD1-Komplexe."Angew. Chem.. 110 (24). 3590-3592 (1998)

Kazuhide Tani、Aika Iseki 和 Tsuneaki Yamagata.：“甲醇的 Leichte 氧化加成和 Peraryldiphosphan-IriiD1-Komplexe”。Angew。110 (24)。

Yasukawa. Kataoka, Atsushi Shibahara, Yoshinori Saito, Tsuneaki Yamagata, and Kazuhide Tani: "Highly Diastereoselective Oxidative Addition of Alkyl Halides to Rhodium and Iridium Carbonyl Complexes Having an ηィイD15ィエD1 : ηィイD11ィエD1 - (Ind-P)n Ligand ((Ind

Kataoka、Atsushi Shibahara、Yoshinori Saito、Tsuneaki Yamagata 和 Kazuhide Tani：“烷基卤化物与具有 η-D15-D1 的铑和铱羰基配合物的高度非对映选择性氧化加成：η-D11-D1 - (Ind-P) n 配体 ((Ind