二甲胺基尾式卟啉铁与双原子小分子CO,NO配位性质的研究

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1.38x10^7M^-^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。

Studies on carbon monoxide and nitric oxide complexes of a new tailed prophyrin iron

FeL(CO) and FeL(NO)]+ (H2L = meso-o-(4-dimethylamino)butyramidophenyl]triphenylporphyrin) were prepared and studied by UV, MCD, EPR, and cyclic voltammetry. The reaction equilibrium constant (1.38 ?107 M-1) of FeL with CO was measured. The 5th ligand affects the equilibrium constant The tailed Fe(II) porphyrin complex is coordinated by NO in the 6th coordination position; the axial coordinated base (tail) is away from Fe because the unpaired electrons of NO has to go into the antibonding orbital of sp3(N) + dz2(Fe). The redox of CO, NO complexes is irreversible and suggests the electrode reaction involving an electron mechanism.