Reactions of carbon dioxide bound to aluminum diimine hydride with borane dimethyl sulfide and ammonia

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The reaction of aluminum bis-formate acenaphthene-1,2-diimine complex [(ArBIG-bian)Al(μ-OC(H)O)2Li(Thf)2] (I) (ArBIG-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene), prepared by binding carbon dioxide by aluminum diimine hydride [(ArBIG-bian)Al(H)2]–[Li(Thf)4]+, with borane dimethyl sulfide and ammonia was studied. The reaction of I with BH3∙SMe2 (1 : 1) in toluene affords the product of hydroboration of one formate group [(ArBIG-bian)Al(μ-OC(H)O)(OB(H)OCH3)Li(Thf)]2 (II), while the reaction of I with BH3∙SMe2 (1 : 2) is accompanied by reduction of both formate groups and gives complex [(ArBIG-bian)Al(OBOCH3)2OLi2(Thf)2BH4]2 (III), methoxyboroxine (CH3OBO)3 and, presumably, compound [(ArBIG-bian)AlOCH3]. The reaction of I with one equivalent of ammonia in THF gives adduct [(ArBIG-bian)Al(NH3)(μ-OC(H)O)2Li(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)).

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作者简介

M. Moskalev

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: skatova@iomc.ras.ru
俄罗斯联邦, Nizhny Novgorod

A. Skatova

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

编辑信件的主要联系方式.
Email: skatova@iomc.ras.ru
俄罗斯联邦, Nizhny Novgorod

A. Bazanov

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: skatova@iomc.ras.ru
俄罗斯联邦, Nizhny Novgorod

E. Baranov

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: skatova@iomc.ras.ru
俄罗斯联邦, Nizhny Novgorod

I. Fedushkin

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: skatova@iomc.ras.ru
俄罗斯联邦, Nizhny Novgorod

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6. Fig. 1. Molecular structure of complex II. Thermal ellipsoids are shown with 30% probability. Hydrogen atoms, except those bonded to C(79), C(80), C(79)′, C(80)′, B(1), and B(1)′ atoms, as well as 2,6-dibenzhydryl-4-methylphenyl substituents at nitrogen atoms, are not shown.

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7. Fig. 2. Molecular structure of complex III. Thermal ellipsoids are shown with 30% probability. Hydrogen atoms, except for those bonded to C(79), C(80), C(79)′, C(80)′, B(1), and B(1)′ atoms, as well as 2,6-dibenzhydryl-4-methylphenyl substituents at nitrogen atoms are not shown.

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8. Fig. 3. Molecular structure of complex IV. Thermal ellipsoids are shown with 30% probability. Hydrogen atoms, except those bound to N(3), C(79), and C(80) atoms, are not shown.

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