Aluminum hydrides with radical-anionic and dianionic acenaphthene-1,2-diimine ligands

Journal Article · Fri Sep 15 04:00:00 EDT 2017 · Russian Chemical Bulletin

DOI:https://doi.org/10.1007/S11172-017-1926-1· OSTI ID:22863518

Sokolov, V. G.; Koptseva, T. S.; Moskalev, M. V.; Piskunov, A. V.; Samsonov, M. A.

The reaction of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) with LiAlH{sub 4} affords two products regardless of the solvent used (tetrahydrofuran or diethyl ether). These products were isolated as green and colorless crystals. Green crystals of the complex [(dpp-bian)Al(H){sub 2}Li(THF){sub 3}] (1) were obtained from tetrahydrofuran; colorless crystals of the complex [{dpp-bian(H_2)}Al(H){sub 2}Li(Et{sub 2}O){sub 2}] (2), from diethyl ether. The reactions of compound 1 with 2,6-di-tert-butyl-4-methylphenol and benzophenone gave monohydrides [(dpp-bian)Al(H)(OC{sub 6}H{sub 2}-2,6-Bu{sub 2}{sup t}-4-Me)][Li(THF){sub 4}] (3) and [(dpp-bian)Al(H)(OCHPh{sub 2})- Li(THF){sub 2}] (4), respectively. The diamagnetic aluminum hydride [(dpp-bian)AlH(THF)] (5) was synthesized by the reaction of dichloroalane HAlCl{sub 2} (in situ) with the disodium salt of dpp-bian in THF; the paramagnetic hydride [(dpp-bian)AlH(Cl)] (6) containing the dpp-bian radical anion was synthesized by the reaction of the monosodium salt (dpp-bian)Na with monochloroalane H{sub 2}AlCl (in situ) in diethyl ether. The reaction of compound 6 with tert-butyllithium gives the complex [(dpp-bian)AlBu{sup t}(Et{sub 2}O)] (7). Diamagnetic derivatives 1—5 and 7 were characterized by {sup 1}Н NMR spectroscopy; paramagnetic compound 6, by ESR spectroscopy. The molecular structures of compounds 1—7 were determined by single-crystal X-ray diffraction.

• OSTI ID: 22863518
• Journal Information: Russian Chemical Bulletin, Journal Name: Russian Chemical Bulletin Journal Issue: 9 Vol. 66; ISSN RCBUEY; ISSN 1066-5285
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ACENAPHTHENE
ALUMINIUM
ALUMINIUM HYDRIDES
ANIONS
BENZOPHENONE
ELECTRON SPIN RESONANCE
ETHYL ETHER
LITHIUM HYDRIDES
MOLECULAR STRUCTURE
MONOCRYSTALS
NUCLEAR MAGNETIC RESONANCE
PARAMAGNETISM
RADICALS
SALTS
SOLVENTS
SPECTROSCOPY
TETRAHYDROFURAN
X-RAY DIFFRACTION