title: Mechanism of the aminolysis of Fischer alkoxy and thiocarbene complexes: a DFT study.
abstract: B3LYP calculations have been carried out to study the reaction mechanism of the aminolysis of Fischer carbene complexes of the type (CO)(5)Cr=C(XMe)R (X = O and S; R = Me and Ph). We have explored different possible reaction mechanisms either through neutral or zwitterionic intermediates as well as a general base catalysis assisted by an ammonia molecule. Our results show that the most favorable pathway for the aminolysis of Fischer carbene complexes is through a stepwise reaction via a zwitterionic intermediate generated by the initial nucleophilic attack. We have found that the ammonia-catalyzed mechanism entails a significantly lower barrier for the rate-determining step than the uncatalyzed one. At lower pressure gas-phase conditions, the rate-determining step corresponds to the concerted proton transfer and MeXH elimination. Thiocarbene complexes show a higher energy barrier for this rate-determining step due to the lower basicity of the MeS(-) substituent. At higher pressure or in solution, the rate-determining step corresponds to the initial nucleophilic attack. Our results indicate that the transition state of the nucleophilic attack is more advanced and has a higher barrier for alkoxycarbene than thiocarbene complexes due to the stronger pi-donor character of the alkoxy group that reduces the electrophilicity of the attacked carbene atom making the nucleophilic attack more difficult.
authors: Instituto de Investigaciones en Fisicoquímica de Córdoba, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, 5016 Córdoba, Argentina.
authors: Diego M
authors: DM
authors: Andrada
authors: J Oscar C
authors: JO
authors: Jimenez-Halla
authors: Miquel
authors: M
authors: Solà
mesh_terms: D000588:Amines / Q000737:chemistry*; D002857:Chromium / Q000737:chemistry*; D003198:Computer Simulation; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D011789:Quantum Theory; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D000588:Amines; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D002857:Chromium; C030011:carbene; D008697:Methane