Kinetics study of the substitution reaction of fac-[Fe(CN)2(CO)3I] with PPh3 |
| |
| Authors: | Benjamin Schwartz Jonathan Solaimanzadeh Wenfeng Lo |
| |
| Institution: | a Department of Chemistry, Yeshiva University, New York, NY 10033, USA
b Department of Chemistry of Chemical Biology, Harvard University, Cambridge, MA 02138, USA |
| |
| Abstract: | Substitution reaction of fac-FeII(CN)2(CO)3I]− with triphenylphosphine (PPh3) produced mono phosphine substituted complex cis-cis-FeII(CN)2(CO)2(PPh3)I]−. Crystal structure of the product showed that carbonyl positioned trans- to iodide was replaced by PPh3. The substitution reaction was monitored by quantitative infrared spectroscopic method, and the rate law for the substitution reaction was determined to be rate = kFeII(CN)2(CO)2(PPh3)I]−]PPh3]. Transition state enthalpy and entropy changes were obtained from Eyring equation k = (kBT/h)exp(−ΔH≠/RT + ΔS≠/R) with ΔH≠ = 119(4) kJ mol−1 and ΔS≠ = 102(10) J mol−1 K−1. Positive transition state entropy change suggests that the substitution reaction went through a dissociative pathway. |
| |
| Keywords: | Cyano Substitution Kinetics Crystal structure |
| 本文献已被 ScienceDirect 等数据库收录！ |
|
