Yamaguchi Motowo, Machiguchi Kazuhiro, Mori Tomonori, Kikuchi Koichi, Ikemoto Isao, Yamagishi Takamichi
Department of Industrial Chemistry, Faculty of Engineering, and Department of Chemistry, Faculty of Science, Tokyo Metropolitan University, Minami-ohsawa, Hachioji, Tokyo 192-03, Japan.
Inorg Chem. 1996 Jan 3;35(1):143-148. doi: 10.1021/ic941264n.
(alpha-Imino acidato)ruthenium(II) complexes, Ru(II){N(R(1))=C(R(2))CO(2)}L(2) (R(1) = R(2) = Me or R(1) = R(2) = -(CH(2))(3)-; L = 2,2'-bipyridine (=bpy) or 1,10-phenanthroline (=phen)), were obtained by anodic oxidation at a constant potential of the corresponding (alpha-amino acidato)ruthenium(II) complexes, N-methylalaninato or prolinato complexes, in good to excellent yields. (alpha-Imino acidato)ruthenium(II) complexes are stable in neutral or acidic aqueous solution. The half-wave potentials of alpha-imino acidato complexes are 0.73-0.78 V (vs SCE), which are more positive than those of the corresponding alpha-amino acidato complexes, 0.55-0.59 V. The crystal structure of [Ru(pro-H(2))(bpy)(2)]ClO(4).3H(2)O (pro-H(2) = 1,2-didehydroprolinato) has been determined by single-crystal X-ray analysis. Crystallographic data: space group C2/c, a = 21.73(1) Å, b = 19.33(1) Å, c = 14.58(1) Å, beta = 114.91(5) degrees, Z = 8, R = 0.0352. The length of the C=N double bond of the alpha-imino acidate moiety is 1.294(5) Å, and Ru-N(imino nitrogen) = 2.042(3) Å. The chelate ring of the alpha-imino acidato ligand is planar.
（α-亚氨基酸根）钌（II）配合物，Ru(II){N(R(1))=C(R(2))CO(2)}L(2)（R(1)=R(2)=甲基或R(1)=R(2)=-(CH(2))(3)-；L = 2,2'-联吡啶（=bpy）或1,10-菲咯啉（=phen）），通过在恒定电位下对相应的（α-氨基酸根）钌（II）配合物、N-甲基丙氨酸根或脯氨酸根配合物进行阳极氧化制得，产率良好至优异。（α-亚氨基酸根）钌（II）配合物在中性或酸性水溶液中稳定。α-亚氨基酸根配合物的半波电位为0.73 - 0.78 V（相对于饱和甘汞电极），比相应的α-氨基酸根配合物的半波电位（0.55 - 0.59 V）更正。[Ru(pro-H(2))(bpy)(2)]ClO(4).3H(2)O（pro-H(2)=1,2-二脱氢脯氨酸根）的晶体结构已通过单晶X射线分析确定。晶体学数据：空间群C2/c，a = 21.73(1) Å，b = 19.33(1) Å，c = 14.58(1) Å，β = 114.91(5)°，Z = 8，R = 0.0352。α-亚氨基酸根部分的C=N双键长度为1.294(5) Å，Ru-N（亚氨基氮）= 2.042(3) Å。α-亚氨基酸根配体的螯合环是平面的。
