A laser flash photolysis, matrix isolation, and DFT investigation of (η6-C6H5Y)Cr(CO)3 (Y=NH2, OCH3, H, CHO, or CO2CH3)
作者:Mohammed A.H. Alamiry、Peter Brennan、Conor Long、Mary T. Pryce
DOI:10.1016/j.jorganchem.2008.06.003
日期:2008.8
from (η6-C6H5Y)Cr(CO)3 was measured in 1,1,2-trifluorotrichloroethane (Y = NH2, OCH3, H, CHO, or CO2CH3). Values of 0.24, 0.27, 0.15, 0.17, and 0.32 were obtained respectively (λexc. = 355 nm). These values are significantly higher than those measured for photoinduced arene loss in hydrocarbon solvents using the same excitation wavelength. Laser flash photolysis of (η6-C6H5Y)Cr(CO)3 in 1,1,2-trifluorotrichloroethane
量子产率从(η芳烃位移6 -C 6 H ^ 5 Y)的Cr(CO)3是在1,1,2-三氟三氯乙烷测量(Y = NH 2,OCH 3,H,CHO,或CO 2 CH 3)。0.24,0.27,分别获得0.15,0.17,和0.32(值λ EXC。 = 355纳米)。这些值明显高于使用相同激发波长在烃类溶剂中光致芳烃损失的测量值。(η的激光闪光光解6 -C 6 H ^ 5 Y)的Cr(CO)3在1,1,2-三氟三氯乙烷(λ EXC。 = 355 nm)导致Cr(CO)6的快速形成(<10 ns)。上(η矩阵隔离实验6 -C 6 H ^ 5 Y)的Cr(CO)3在12 K的CH(Y = H或CHO)4或CO-CH掺杂4点矩阵使用单色的照射证实两个分立的激发态的存在,一种导致CO损失,另一种导致芳烃损失。结果与根据密度泛函理论和时间相关的密度泛函理论计算得出的激发态电子漂移相关。