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Citation: Zhang Qiyan*, Zhu Chengyue, Song Licheng, Chen Rongti. STUDY ON THE KINETICS AND MECHANISMS OF THE SUBSTITUTION REACTIONS OF SOME DI-ALKYLTHIOLATOHEXACARBONYLDIIRON COMPLEXES[J]. Acta Physico-Chimica Sinica, ;1988, 4(02): 152-158. doi: 10.3866/PKU.WHXB19880208 shu

STUDY ON THE KINETICS AND MECHANISMS OF THE SUBSTITUTION REACTIONS OF SOME DI-ALKYLTHIOLATOHEXACARBONYLDIIRON COMPLEXES

1.
Department of Chemistry; Nankai University; Tianjin

Received Date: 30 August 1986
Available Online: 15 April 1988

The kinetics and mechanisms of the substitution reactions of (μ,μ-SCH_2S)Fe_2 (CO)_6 with PPh_3, PMe_2Ph, PEt_3, P(n-Bu)_3 and (μ-PhCH_2S)(μ-RS)Fe_2(CO)_6(R=Me, Et) with PPh_3 in various solvents have been studied by means of UV-spectra and ~1H NMR. The results support the mechanism of Ia (associative interchange) for the substitution reactions of first step and Id (dissociative interchange) for the reactions of second step. The electronic effects of the ligands, steric effects of the ligands and the parent complexes and the solvent effecs on the reaction rates have been discussed. It shows that the reaction rate is presumably determined by the volume of the incoming ligands. the nucleophilic solvents such as DMF can promote the reaction rate by means of base catalysis.
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