摘要
本文报道了二甲胺基尾式卟啉铁{中位-[邻(4-二甲胺基丁酰胺基)苯基]三苯基卟啉合铁(Ⅱ)}同双原子小分子CO,NO的配合物的UV,MCD,ESR光谱和电化学性质,测定了它与CO轴向加合平衡常数为1.38×10~7M^(-1),讨论了尾端配体对CO与中心离子铁的成键影响。NO配合物的,ESR和循环伏安结果表明,NO的配位削弱了尾端N与中心离子铁的键强,并用分子轨道理论解释了这一结果。
The carbon monoxide and nitric oxide adducts of meso-mono [o-(4-dimethylamino) butyramidophenyl] triphenylporphyrin iron (Ⅱ) were prepared and studied by UV, MCD, EPR and cyclic voltammetry. The reaction equilibrium constant (1.38×10~7 M^-1) of PFe(Ⅱ) with CO was measured. The results demonstrate that (1) the fifth ligand affects the equilibrium constant considerably. (2) the tailed iron (Ⅱ) porphyrin complex is coordinated by NO in the sixth coordination position, the axial coordinated base (tail) is away from iron because the unpaired electrons of NO has to go into the antibonding orbital of sp^3(N)+d_(?)(Fe). (3) The redox of CO, NO complexes is irreversible and suggests the electrode reaction involving an EC mechanism.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
1990年第5期459-465,共7页
Acta Chimica Sinica
基金
国家自然科学基金
