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利用高温高压动力学实验和“原位”红外技术研究了三种代表性硫化物(硫化氢、单质硫、正丙硫醇)对铑膦络合物催化的丙烯氢甲酰化反应的影响及其作用机理。实验表明,各种硫化物同铑膦络合物的配位作用以及与配体三苯基膦反应生成硫化三苯基膦的作用是硫致失活的根本原因,各种硫化物行为的差异可归结为其硫原子亲电性的大小。
The hydroformylation of propylene catalyzed by rhodium-phosphine complexes with three representative sulfides (hydrogen sulfide, elemental sulfur, n-propanethiol) was studied using high temperature and high pressure kinetics experiments and “in situ” infrared techniques Influence and its mechanism of action. The experimental results show that the coordination of various sulfides with rhodium-phosphine complexes and the reaction with triphenylphosphine ligand to form triphenylphosphine sulfide are the fundamental causes of sulfur-induced deactivation. The differences of various sulfide behaviors Can be attributed to the size of its sulfur atom electrophilic.