Examination of a dicationic rhodium methyl aquo complex
摘要:
A cationic rhodium aquo methyl complex, [Rh(bpy)(CH3)(H2O)(3)](2+)center dot 2[BF4], was prepared and examined for activity related to the Shilov PtII system, specifically the formation of methanol. Instead, the complex exhibited interesting behavior under basic conditions, with rare double "rollover" metalation of the coordinated bipyridine ligand and deuterium incorporation into the rhodium methyl group. (C) 2012 Elsevier B. V. All rights reserved.
已经制备了一系列Rh(I)配合物[Rh(CO)(diimine)I](diimine = ArN C(Me)C(Me)NAr,Ar = 2- i PrC 6 H 4(1a),2, 4,6-Me 3 C 6 H 2(1b),2,6- i Pr 2 C 6 H 3(1c);二亚胺= ArN C(Me)-2-py,Ar = C 6 H 5(1d) ,2- i PrC 6 H 4(1e),2,6- i Pr 2 C6 H 3(1f);二亚胺= 2,2'-bipy(1g))。X射线晶体结构显示1f具有CO反式至吡啶基氮。将MeI氧化添加到1a,d,e,g中得到稳定的甲基络合物[Rh(CO)(diimine)I 2 Me](分别为2a,d,e,g);2a的X射线结构显示出伪八面体的几何结构,其中甲基转化为碘化物。相反,1b,c的反应用MeI得到五配位的乙酰基络合物[Rh(二亚胺)I 2(COMe)](