Nagao Hirotaka, Hirano Toshiyuki, Tsuboya Naotoshi, Shiota Soni, Mukaida Masao, Oi Takao, Yamasaki Mikio
Department of Chemistry, Faculty of Science and Technology, Sophia University, Tokyo 102-8554, Japan.
Inorg Chem. 2002 Dec 2;41(24):6267-73. doi: 10.1021/ic011241q.
The reaction of cis-Ru(NO)(CH(3)CN)(bpy)(2) (bpy = 2,2'-bipyridine) in H(2)O at room temperature proceeded to afford two new nitrosylruthenium complexes. These complexes have been identified as nitrosylruthenium complexes containing the N-bound methylcarboxyimidato ligand, cis-Ru(NO)(NH=C(O)CH(3))(bpy)(2), and methylcarboxyimido acid ligand, cis-Ru(NO)(NH=C(OH)CH(3))(bpy)(2), formed by an electrophilic reaction at the nitrile carbon of the acetonitrile coordinated to the ruthenium ion. The X-ray structure analysis on a single crystal obtained from CH(3)CN-H(2)O solution of cis-Ru(NO)(NH=C(O)CH(3))(bpy)(2)(3) has been performed: C(22)H(20.5)N(6)O(2)P(2.5)F(15)Ru, orthorhombic, Pccn, a = 15.966(1) A, b = 31.839(1) A, c = 11.707(1) A, V = 5950.8(4) A(3), and Z = 8. The structural results revealed that the single crystal consisted of 1:1 mixture of cis-Ru(NO)(NH=C(O)CH(3))(bpy)(2) and cis-Ru(NO)(NH=C(OH)CH(3))(bpy)(2) and the structural formula of this single crystal was thus Ru(NO)(NH=C(OH(0.5))CH(3))(bpy)(2)(2.5). The reaction of cis-Ru(NO)(CH(3)CN)(bpy)(2) in dry CH(3)OH-CH(3)CN at room temperature afforded a nitrosylruthenium complex containing the methyl methylcarboxyimidate ligand, cis-Ru(NO)(NH=C(OCH(3))CH(3))(bpy)(2). The structure has been determined by X-ray structure analysis: C(25)H(29)N(8)O(18)Cl(3)Ru, monoclinic, P2(1)/c, a = 13.129(1) A, b = 17.053(1) A, c = 15.711(1) A, beta = 90.876(5) degrees, V = 3517.3(4) A(3), and Z = 4.
顺式-[Ru(NO)(CH₃CN)(bpy)₂]³⁺（bpy = 2,2'-联吡啶）在室温下于水中反应，生成了两种新的亚硝酰钌配合物。这些配合物已被鉴定为含有N-键合甲基羧基亚氨基配体的亚硝酰钌配合物，即顺式-[Ru(NO)(NH=C(O)CH₃)(bpy)₂]²⁺，以及甲基羧基亚氨基配体，即顺式-[Ru(NO)(NH=C(OH)CH₃)(bpy)₂]³⁺，它们是通过与钌离子配位的乙腈的腈基碳上的亲电反应形成的。对从顺式-Ru(NO)(NH=C(O)CH₃)(bpy)₂₃的CH₃CN - H₂O溶液中获得的单晶进行了X射线结构分析：C₂₂H₂₀.₅N₆O₂P₂.₅F₁₅Ru，正交晶系，Pccn，a = 15.966(1) Å，b = 31.839(1) Å，c = 11.707(1) Å，V = 5950.8(4) ų，Z = 8。结构结果表明，单晶由顺式-[Ru(NO)(NH=C(O)CH₃)(bpy)₂]²⁺和顺式-[Ru(NO)(NH=C(OH)CH₃)(bpy)₂]³⁺的1:1混合物组成，因此该单晶的结构式为Ru(NO)(NH=C(OH(0.5))CH₃)(bpy)₂₂.₅。顺式-[Ru(NO)(CH₃CN)(bpy)₂]³⁺在室温下于干燥的CH₃OH - CH₃CN中反应，得到了一种含有甲基甲基羧基亚氨基配体的亚硝酰钌配合物，即顺式-[Ru(NO)(NH=C(OCH₃)CH₃)(bpy)₂]³⁺。其结构已通过X射线结构分析确定：C₂₅H₂₉N₈O₁₈Cl₃Ru，单斜晶系，P2₁/c，a = 13.129(1) Å，b = 17.053(1) Å，c = 15.711(1) Å，β = 90.876(5)°，V = 3517.3(4) ų，Z = 4。
