紫外可见分光光度法研究金属卟啉与Lewis碱性溶剂的轴向配位作用.pdfVIP

( ) 2002 12 ACT A PETROLEI SINICA (PETROLEUM PROCESSING SECT ION) 18 6 : 1001-8719( 2002)06-0061-06 Lewis STUDY ON AXIAL COORDINATION OF METALLOPORPHYRINS WITH LEWIS BASES BY UV-VIS SPECTROPHOTOMETRY 徐 海, 于道永, 阙国和, 王宗贤 U Hai, YU Dao-yong, QUE Guo-he, WANG Zong-xian ( , , 257061) ( I nsti tu te of Chemist ry Che mical Engi neering , Univ ers ity of Petr oleu m , Dongy i ng, 257061, Chi na) : -( VOT PP) -( NiTPP) Lewis , Lewis , ; d , VOT PP NiTPP Lewis ; Lewis () : ; Lewis ; ; : O64114 : A Abstra t: T he axial interaction of vanadyl meso-tetraphenylporphyrin (VOTPP) and nickel meso-te- traphenylporphyrin (NiTPP) with different Lewis basic solvents was investigated by using an ultravi- olet-visible ( UV-Vis) spectrophotometric method. The B and Q bands, the characteristic bands of the two metalloporphyrins, undergo bathochromic shift in some of the Lewis basic solvents. The spectral changes are thought to be due to the axial coordination of these solvents with vanadium in VOTPP and nickel in NiTPP. After axial coordination, the energy gap between LUMOs ( e g) and HOMOs ( A , A ) of porphyrin ring decreases. T he axial interaction is related to thenumber of the 1L 2L d electrons on the central metal, the electron donating ability, and the steric structure of Lewis basic solvent. The electron accepting ability of V( Ô) with one d electron is stronger than that of Ni( Ò) with eight d electrons, so VOTPP coordinates more easily with Lewis Bases than NiTPP. The sol- vent, such as n-butylamine, which has strong electron donating ability and is almost sterically unen- cumbered, is liable to coordinate with Lewis bases. Key words: metalloporphyrins; Lewis basic solvents; axial c