Magnesium and Calcium Complexes of Ar^BIG‐bian and Their Reactivity towards CO₂ (Ar^BIG‐bian=1,2‐bis[(2,6‐dibenzhydryl‐4‐methylphenyl)imino]acenaphthene)

Abstract

Abstract Reduction of 1,2‐bis[(2,6‐dibenzhydryl‐4‐methylphenyl)imino]acenaphthene (Ar BIG ‐bian) with an excess of magnesium in tetrahydrofuran (thf) or with an excess of calcium in 1,2‐dimethoxyethane (dme) and crystallization of the crude products from the reaction mixtures affords monomeric complexes [(Ar BIG ‐bian)Mg(thf) 2 ] ( 1 ) or [(Ar BIG ‐bian)Ca(dme) 2 ] ( 2 ), respectively. Hydrolysis of complex 1 affords metal‐free diamine [Ar BIG ‐bianH 2 (thf)] ( 3 ). Complexes 1 and 2 readily react with CO 2 to form the corresponding carbamates [(Ar BIG ‐bian)(CO 2 ) 2 Mg(thf) 2 ] ( 4 ) and [(Ar BIG ‐bian)(CO 2 ) 2 Ca(dme) 2 ] ( 5 ). Compounds 1 – 5 have been characterized by NMR and IR spectroscopy as well as elemental analysis. The molecular structures of 1 , 2 , 3 , and 5 have been determined by the single crystal X‐ray analysis.