Investigation of reactive intermediates during the synthesis of di-n-butylmagnesium

• Published in: Inorganica Chimica Acta Vol. 489; pp. 150 - 154
• Main Authors: Nune, Satish K., Lao, David B., Bowden, Mark E., Schaef, Herbert T., Vemuri, Rama S., Motkuri, Radha Kishan, McGrail, B. Peter
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01.04.2019; Elsevier Science Ltd
• Subjects: Butyllithium; Dialkylmagnesium; Energy dispersive X ray spectroscopy; Grignard reagent; Intermediate; Magnesium chloride; Reaction intermediates; Schlenk equilibrium; Transmetalation; X ray powder diffraction; X-ray diffraction; Dialkylmagnesium; Grignard reagent; Schlenk equilibrium; Intermediate; Transmetalation
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2019.01.035

Energy-dispersive X-ray spectroscopy (EDX) and powder X-ray diffraction (PXRD) were used to characterize the products and the reaction intermediates involved in transmetalation of anhydrous magnesium chloride and n-butyllithium. [Display omitted] •Transmetalation reaction between anhydrous MgCl2 and n-BuLi was studied.•Powder X-ray diffraction (PXRD) was used to characterize the reaction products and intermediates.•Organic solvent was used to shift the Schlenk equilibrium. Dialkylmagnesium compounds (MgR2, R = C2H5, C4H9 etc.,) have drawn considerable interest in recent years due to their role in commercial polymerization reactions. Herein, we report a thorough account on the reaction intermediates involved in the synthesis of di-n-butylmagnesium from anhydrous magnesium chloride and n-butyllithium. Energy-dispersive X-ray spectroscopy (EDX) and powder X-ray diffraction (PXRD) were used to characterize the products formed in transmetalation reaction and it supports that the Schlenk equilibrium between the nBuMgCl and nBu2Mg may be operating during the synthesis of di-n-butylmagnesium from anhydrous magnesium chloride. 1,4-Dioxane was used to shift the Schlenk equilibrium to form soluble 1,4-dioxane adduct of di-n-butylmagnesium and insoluble MgCl2 based product. PXRD was used to study the transformation of 1,4-dioxane adduct of di-n-butylmagnesium to pure di-n-butylmagnesium.