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Intramolecular Non-covalent Interactions in Metal Complexes : Geometrical Controles and Stereoselective Reactions

金属配合物中的分子内非共价相互作用：几何控制和立体选择性反应

基本信息

批准号：
62430011
负责人：
OKAWA Hisashi
金额：
$ 10.5万
依托单位：
Kyushu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1990
项目状态：
已结题

项目摘要

Stereoselectivities of six-coordinate complexes of 4- (l-menthyloxy) -1-phenyl-1, 3-butanedione (H (l-moba) ) and 4- (l-menthyloxy) -1-p-tolly-1, 3-butanedione (H (l-moba-Me) ) have been examined for various metal ions (Co, Cr, Mn, IIIA, IIIB, Ianthanoid). In particular the complexes of IIIA and IIIB ions were studied by means of 400 MHz H-NMR and CD spectroscopies. All the complexes showed a stereoselectivity to afford the fac-OMEGA from predominantly because of the operation of a non-covalent interaction in the from of a left-handed three-bladed propeller, comprising three interligand l-menthyl/aryl contact. The interligand contact became efficient when the central metal ion was significantly large (r>l.OA^^ﾟ).Such sterically controlled lanthanoid complexes Ln (l-moba-Me)_3 were used as Lewis acid catalysts for enantioselective reductions of ketones. Acetophenone was converted into (S) -alcohol (e e % 84) whereas butane-2-one and octane-2-one were converted into (R) -alchols.Stereose … More lectivities of tetrahedral or pseudo-tetrahedral Co (II), Cu- (II), and Zn (II) complexes of N- (l-menthyl) salicylaldimine (H (sal-ment) ) and N- (R) -alpha-methylbenzylsalicylaldimine (H (sal-Rmb) ) have been studied by single-crystal X-ray method, CD spectroscopy, and molecular mechnics Calculations. The preferred configuration was DELTA for tetrahedral [M (sal-ment)_2] (M=Co, Cu, Zn), OMEGA for tetrahedral [M (sal-Rmb)_2] (M=Co, Zn), and DELTA for pseudo-tetrahedral [Cu (sal-Rmb)_2]. The X-ray structural analyses for [M (sal-Rmb)_2] clearly demonstrated the operation of non-covalent interactions between the chiral N-substituent and the adjacent ring. The Cotton effect induced at the azomethine pi-pi^* transition was well correlated with the absolute configration about the metal center.Stereoselectivities of planar metal (II) complexes (M=Cu, Pb, Pt)) of N-substituted ethylenediamines, N- { (R) -alpha-methylbenzyl} ethylenediamine (R-mben), N- { (S) -alpha-methylbenzyl} ethylenediamine (S-mben), and N- (l-menthyl) -ethylenediamine (mten), have been examined by electronic absorption and CD spectroscopies and interpreted based on a regional rule (hexadecadalrule). The preferred conformation with respect to the ethylene chain were delta for the mten and B-mben complexes and lambda for the S-mben complexes. Less

本文研究了4-（1-孟氧基）-1-苯基-1，3-丁二酮（H（1-moba））和4-（1-孟氧基）-1-对甲苯基-1，3-丁二酮（H（1-moba-Me））六配位配合物对多种金属离子（Co，Cr，Mn，IIIA，IIIB，镧系元素）的立体选择性。特别是IIIA和IIIB离子的配合物通过400 MHz H-NMR和CD光谱进行了研究。所有的配合物显示出立体选择性，以提供fac-OMEGA从主要是因为操作的非共价相互作用的形式的左手三叶片螺旋桨，包括三个interligand 1-薄荷基/芳基接触。当中心金属离子较大时（r> 1.0A），配体间的接触变得有效，这种空间可控的稀土配合物Ln（l-moba-Me）_3可用作刘易斯酸催化剂，催化酮的不对称还原反应。苯乙酮转化为（S）-醇（e % 84），而丁烷-2-酮和辛烷-2-酮转化为（R）-醇。 ...更多信息用单晶X射线衍射、圆二色谱和分子力学计算等方法研究了N-（1-薄荷基）水杨醛亚胺（H（sal-ment））和N-（R）-α-甲基苄基水杨醛亚胺（H（sal-Rmb））的四面体或拟四面体Co（II）、Cu（II）和Zn（II）配合物的选择性。四面体[M（sal-ment）_2]（M=Co，Cu，Zn）的优选构型为DELTA，四面体[M（sal-Rmb）_2]（M=Co，Zn）的优选构型为OMEGA，假四面体[Cu（sal-Rmb）_2]的优选构型为DELTA。[M（sal-Rmb）_2]的X-射线结构分析清楚地证明了手性N-取代基与相邻环之间的非共价相互作用。偶氮甲碱π-π ^* 跃迁引起的Cotton效应与金属中心的绝对取代度密切相关。平面金属配合物的立体选择性（M=Cu，Pb，Pt））、N- {（R）-α-甲基苄基}乙二胺（R-mben）、N- {（S）-α-甲基苄基}乙二胺（S-mben）和N-{（R）-α-甲基苄基}乙二胺（S-mben）。（l-薄荷基）-乙二胺（mten）的电子吸收和CD光谱进行了研究，并根据区域规则（十六进制规则）进行了解释。相对于乙烯链的优选构象是δ的mten和B-mben复合物和λ的S-mben复合物。少

项目成果

期刊论文数量（67）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Naohisa Kumagai: "Cobalt(III) Mixedーchelates with Tetradentate N,N′ーBis(1ーlーMenthyloxyー3ーbenzoylacetone)ethylenediimine and Bidentate Chelate.Controle of Chelate Conformation by Bidentata Ligand" Mem.Fac.Sci.,Kyushu Univ.,Ser.C,. 17(1). 69-72 (1989)

Naohisa Kumagai：“Cobalt(III) Mixed-chelates with Tetradentate N,N′-Bis(1-Menthyloxy-3-Benzylacetone)乙二亚胺和Bidentate Chelate.Controle of Chelate Conformation by Bidentata Ligand”九州大学Mem.Fac.Sci. .，C，17(1)。