Abstract

Carbocyclic aluminium halides [(ADC)AlX2 ]2 (2-X) (X=F, Cl, and I) based on an anionic dicarbene (ADC=PhC{N(Dipp)C}2 , Dipp = 2,6-iPr2 C6 H3 ) framework are prepared as crystalline solids by dehydrohalogenations of the alane [(ADC)AlH2 ]2 (1). KC8 reduction of 2-I affords the peri-annulated Al(III) compound [(ADCH )AlH]2 (4) (ADCH= PhC{N(Dipp)C2 (DippH )N}, DippH =2-iPr,6-(Me2 C)C6 H3 )) as a colorless crystalline solid in 76 % yield. The formation of 4 suggests intramolecular insertion of the putative bis-aluminylene species [(ADC)Al]2 (3) into the methine C-H bond of HCMe2 group. Calculations predict singlet ground state for 3, while the conversion of 3 into 4 is thermodynamically favored by 61 kcal/mol. Compounds 2-F, 2-Cl, 2-I, and 4 have been characterized by NMR spectroscopy and their solid-state molecular structures have been established by single crystal X-ray diffraction.

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