Com putation al investigation of plausible s pecies in l inkage isomerization of nitro- and nitrito-pen taamminecobalt(III) complexes

Linkage isomerism is observed in coordination co mpounds when an am bidentate ligand (e.g.,N O۲-) binds t he metal center through the one or t he other of its two terminal donor atoms, giving rise to two different complexes. A well-know n classic ex ample in this sense refers to the nitro/nitrito isomerism in complexes of penta amminecoba lt(III). The kinetic and the thermodynamic of the spontaneous iso merization of correspo nding complexes have been studied both in solution and s olid state [۱ -۳]. This reaction was p roved to be intramolecular by differ ent experim ental techni ques. The n ature of tran sition state and deeper understanding of reacti on mechanism using e xperimental data are still unanswe red. Hence, in this st udy a quant um mechanical approac h was emplo yed to elucidate the electronic struc ture of nitro - and nitritopentaammin e cobalt(III) complexes (as shown in Fig.۱) an d its transiti on state. Also, the thermodynamic a nd kinetic data of the i somerization was evaluated using the computational methods.

کلیدواژه ها:

DFT ، Linkage Isomer ، Nitro ، Nitrito ، Thermodynamic ، Kinetic