Photolysis of Isoelectronic Ruthenium Nitrosyl and Diazonium Complexes in Frozen PVC Matrices: Retention of Dinitrogen on Ruthenium Following Photochemical Phenyl Radical Loss
作者:Wyatt A. Thornley、Thomas E. Bitterwolf
DOI:10.1002/ejic.201501100
日期:2016.2
Photolysis of RuCl3(1-NO)(PPh3)2 in poly(vinyl chloride) (PVC) matrices at 85 K results in reversible linkage isomerism of the nitrosyl ligand to form the isonitrosyl complex RuCl3(1-ON)(PPh3)2. Metal-to-ligand charge-transfer (MLCT) excitation of the isoelectronic phenylazo complex, RuCl3(1-N2Ph)(PPh3)2, has previously been shown to result in generation of the phenyl radical, presumably through decomposition
聚氯乙烯 (PVC) 基质中 RuCl3(1-NO)(PPh3)2 在 85 K 下的光解导致亚硝酰基配体的可逆连接异构现象,形成异亚硝酰基复合物 RuCl3(1-ON)(PPh3)2。等电子苯偶氮络合物 RuCl3(1-N2Ph)(PPh3)2 的金属到配体电荷转移 (MLCT) 激发先前已被证明会导致苯自由基的产生,推测是通过分解光生二氮烯自由基。在低温下对 PVC 基质中的这种光解进行检查,可以直接观察同位素敏感的产物带,该带可能属于 17 电子钌二氮物种,