溶液中(RC_2R!')CO(CO)(PR_3~')_2的配体PR_3~'之间的交换作用——三跳动力学模型

CHEMICAL EXCHANGE OF LIGAND PR_3″ OF (RC_2R′) Co (CO) (PR_3″)_2 IN SOLUTION TRIPLE-JUMP KINETIC MODEL

本文成功地运用了三跳动力学模型,通过相关函数和超精细分裂常数的关系,推出了电子自旋共振波谱的线宽与基本线宽T_(2,0)^(-1)、溶液中各种异构体的超精细分裂常数、配体的交换寿命等之间的关系。求出了在290K温度下(Ph_2C_2)Co(CO)[P(OEt)_3]_2的THF溶渡中P(OEt)_3配体的交换寿命是5.6×10^(-11)秒。

This paper described a detailed theoretical analysis of ESR spectrum line width of the cobalt complex (RC_2R/)Co(CO)(PR'_3)_2 in solution. Triple-jump kinetic model was first used in the Trans-Cis isomerism of the complex.A formula concerning ESR line width as a function of the basic line width T_(20)^(-1), hyperfine splitting constants of all isomers in solution, and lifetime of the exchange of ligand PR'_3 were suggested on the relationship between the correlation function and the hyperfine splitting constant. The calculated, exchange lifetime of the ligand P(OEt)_3 in the title complex (Ph_2C_2)Co(CO)[P(OEt)_3]_2 at 290 K is 5.6×10^(-11)s.