Tejel Cristina, Ciriano Miguel A, Bordonaba Marta, López José A, Lahoz Fernando J, Oro Luis A
Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain.
Inorg Chem. 2002 May 6;41(9):2348-55. doi: 10.1021/ic0109952.
The reactions of [M(mu-OMe)(cod)] (M = Rh, Ir; cod = 1,5- cyclooctadiene) with p-tolylamine, alpha-naphthylamine, and p-nitroaniline gave complexes with mixed-bridging ligands, [M(cod)(mu-NHAr)(mu-OMe)]. Similarly, the related complexes [Rh(cod)(mu-NHAr)(mu-OH)] were prepared from the reactions of [Rh(mu-OH)(cod)] with p-tolylamine, alpha-naphthylamine, and p-nitroaniline. The reactions of [Rh(mu-OR)(cod)] (R = H, Me) with o-nitroaniline gave the mononuclear complex [Rh(o-NO(2)C(6)H(4)NH)(cod)]. The syntheses of the amido complexes involve a proton exchange reaction from the amines to the methoxo or hydroxo ligands and the coordination of the amide ligand. These reactions were found to be reversible for the dinuclear complexes. The structure of [Rh(cod)(mu-NH[p-NO(2)C(6)H(4)])(mu-OMe)] shows two edge-shared square-planar rhodium centers folded at the edge with an anti configuration of the bridging ligands. The complex [Rh(cod)(mu-NH[alpha-naphthyl])(mu-OH)] cocrystallizes with [Rh(mu-OH)(cod)] and THF, forming a supramolecular aggregate supported by five hydrogen bridges in the solid state. In the mononuclear [Rh(o-NO(2)C(6)H(4)NH)(cod)] complex the o-nitroamido ligand chelates the rhodium center through the amido nitrogen and an oxygen of the nitro group.
[M(μ-OMe)(cod)]（M = Rh，Ir；cod = 1,5-环辛二烯）与对甲苯胺、α-萘胺和对硝基苯胺反应生成了带有混合桥联配体的配合物[M(cod)(μ-NHAr)(μ-OMe)]。类似地，相关配合物[Rh(cod)(μ-NHAr)(μ-OH)]是由[Rh(μ-OH)(cod)]与对甲苯胺、α-萘胺和对硝基苯胺反应制备而成。[Rh(μ-OR)(cod)]（R = H，Me）与邻硝基苯胺反应生成单核配合物[Rh(o-NO₂C₆H₄NH)(cod)]。酰胺基配合物的合成涉及胺到甲氧基或羟基配体的质子交换反应以及酰胺配体的配位。发现这些反应对于双核配合物是可逆的。[Rh(cod)(μ-NH[p-NO₂C₆H₄])(μ-OMe)]的结构显示两个边缘共享的平面正方形铑中心在边缘处折叠，桥联配体呈反式构型。配合物[Rh(cod)(μ-NH[α-萘基])(μ-OH)]与[Rh(μ-OH)(cod)]和THF共结晶，在固态下形成由五个氢键支撑的超分子聚集体。在单核[Rh(o-NO₂C₆H₄NH)(cod)]配合物中，邻硝基酰胺配体通过酰胺氮和硝基的一个氧原子螯合铑中心。
