Reaction of a (Salen)ruthenium(VI) Nitrido Complex with Isocyanide

The treatment of [RuVI(N)(L)(MeOH)]PF6 (1) (L = N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion) with 2 equiv of RNC (R = (a) tBu, (b) Cy) in CH2Cl2 affords a mixture of blue cis-β-[RuIII(NCNR)(L)(CNR)] (2) and green trans-[RuIII(L)(CNR)2]PF6 (3) products. The reduction of 3 with a stoichiometric amount of Cp2Co in CH3CN gives red trans-[RuII(L)(CNR)2] (4). Refluxing 4 with 3 equiv of RNC in methanol in the presence of 5 equiv of NH4PF6 affords a yellow complex, mer-[RuII(η3-HL)(CNR)3](PF6) (5), in which the ligand is in an η3-coordination mode. These complexes are characterized by IR, UV−vis, ESI-MS, CV, magnetic measurements, and CHN elemental analysis. The structures of 2a, 3a, 4a, 4b, and 5a have been determined by X-ray crystallography.

将六氟磷酸(甲醇)(氮)(N,N'-双(水杨亚基)-o-环己二胺二阴离子)合钌(VI) (1)（其中配体L = N,N'-双(水杨亚基)-o-环己二胺二阴离子）与2当量的异腈（RNC，R分别为(a)叔丁基(tBu)、(b)环己基(Cy)）在二氯甲烷(CH2Cl2)中反应，得到蓝色顺式-β构型的[RuIII(NCNR)(L)(CNR)] (2)与绿色反式-[RuIII(L)(CNR)2]PF6 (3)的混合物。以化学计量比的二茂钴(Cp2Co)在乙腈(CH3CN)中还原3，可得到红色反式-[RuII(L)(CNR)2] (4)。将4与3当量的异腈在甲醇(MeOH)中、5当量六氟磷酸铵(NH4PF6)存在的条件下回流反应，得到黄色配合物面式(mer)-[RuII(η³-HL)(CNR)3](PF6) (5)，该配合物中配体以η³-配位模式结合。通过红外光谱(IR)、紫外-可见光谱(UV−vis)、电喷雾电离质谱(ESI-MS)、循环伏安法(CV)、磁学测量及碳氢氮(CHN)元素分析对所有配合物进行了表征。通过X射线单晶衍射(X-ray crystallography)确定了2a、3a、4a、4b及5a的晶体结构。