C‐O Bond Cleavage of Diethyl Ether and Tetrahydrofurane by [(dpp‐BIAN)AlI(Et 2 O)] [dpp‐BIAN = 1,2‐bis[(2,6‐di‐iso‐propylphenyl)‐imino]acenaphthene]

At elevated temperatures, the aluminum complex [(dpp‐BIAN)AlI(Et 2 O)] ( 1 ) splits the C‐O bonds of diethyl ether and tetrahydrofurane yielding the dimeric alkoxides [(dpp‐BIAN)AlOEt] 2 ( 2 ) and [(dpp‐BIAN)AlO(CH 2 ) 4 I] 2 ( 3 ), respectively. Already at ambient temperatures, a cleavage of the C‐O bond of THF is to observe in the reaction of 1 with CpNa in THF as confirmed by the formation of [(dpp‐BIAN)AlO(CH 2 ) 4 C 5 H 5 ] 2 ( 4a ) and [(dpp‐BIAN)Al{O(CH 2 ) 4 C 5 H 5 }(THF)] ( 4b ) in a molar ratio of 1:2. The reaction of 1 with t ‐BuOK affords the monomeric alkoxide [(dpp‐BIAN)AlO‐ t ‐Bu(Et 2 O)] ( 5 ). Compounds 2 , 3 , and 4a/b were characterized by elemental analyses and IR spectra. Additionally, the structures of 2 and 3 were determined by single crystal X‐ray diffraction.