Reactions of Carbon Dioxide Bound to Aluminum Diimine Hydride with Borane Dimethyl Sulfide and Ammonia

The reaction of aluminum bis-formate acenaphthene-1,2-diimine complex [(Ar BIG -bian)Al(μ-OC(H)O) 2 Li(Thf) 2 ] ( I ) (Ar BIG -bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene), prepared by binding carbon dioxide by aluminum diimine hydride [(Ar BIG -bian)Al(H) 2 ] – [Li(Thf) 4 ] +...

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Published in:Russian journal of coordination chemistry 2024-02, Vol.50 (2), p.118-129
Main Authors: Moskalev, M. V., Skatova, A. A., Bazanov, A. A., Baranov, E. V., Fedushkin, I. L.
Format: Article
Language:English
Subjects:
Aluminum
Ammonia
Ammonolysis
Boranes
Carbon dioxide
Chemical analysis
Chemical bonds
Chemistry
Chemistry and Materials Science
Diimide
Dimethyl sulfide
Hydrides
Hydroboration
Infrared spectroscopy
Inorganic Chemistry
NMR spectroscopy
Physical Chemistry
Toluene
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Summary:The reaction of aluminum bis-formate acenaphthene-1,2-diimine complex [(Ar BIG -bian)Al(μ-OC(H)O) 2 Li(Thf) 2 ] ( I ) (Ar BIG -bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene), prepared by binding carbon dioxide by aluminum diimine hydride [(Ar BIG -bian)Al(H) 2 ] – [Li(Thf) 4 ] + , with borane dimethyl sulfide and ammonia was studied. The reaction of I with BH 3 ∙SMe 2 (1 : 1) in toluene affords the product of hydroboration of one formate group [(Ar BIG -bian)Al(μ-OC(H)O)(OB(H)OCH 3 )Li(Thf)] 2 ( II ), while the reaction of I with BH 3 ∙SMe 2 (1 : 2) is accompanied by reduction of both formate groups and gives complex [(Ar BIG -bian)Al(OBOCH 3 ) 2 OLi 2 (Thf) 2 BH 4 ] 2 ( III ), methoxyboroxine (CH 3 OBO) 3 and, presumably, compound [(Ar BIG -bian)AlOCH 3 ]. The reaction of I with one equivalent of ammonia in THF gives adduct [(Ar BIG -bian)Al(NH 3 )(μ-OC(H)O) 2 Li(Thf) 2 ] ( IV ), in which ammonia is coordinated to the aluminum atom, while the key bonds in I have not undergone ammonolysis. Compounds II – IV were characterized by IR and NMR spectroscopy, elemental analysis, and X-ray diffraction (CCDC no. 2255017 ( II ), 2255018 ( III ), 2255019 ( IV )).
ISSN:1070-3284
1608-3318
DOI:10.1134/S1070328423600936