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Synthesis and Structural Characteristics of Discrete Organoboron and Organoaluminum Hydrides Incorporating Bulky Eind Groups

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† Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University, 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan
‡ Functional Elemento-Organic Chemistry Unit, RIKEN Advanced Science Institute (ASI), 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
∥ Materials Characterization Support Unit, RIKEN Center for Emergent Matter Science (CEMS), 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
*E-mail: [email protected]
Cite this: Organometallics 2016, 35, 19, 3397–3405
Publication Date (Web):September 26, 2016
https://doi.org/10.1021/acs.organomet.6b00633
Copyright © 2016 American Chemical Society
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    Abstract

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    The bulky Eind-based aryllithium, (Eind)Li (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl), reacted with BF3·OEt2 in Et2O to form the corresponding aryldifluoroborane (Eind)BF2 (1), along with a trace amount of the sterically congested diarylborane, (Eind)2BH (2). The reaction of 1 with LiAlH4 in THF led to the isolation of the corresponding lithium trihydroborate [Li(thf)]2[(Eind)BH3]2 (3), which can be transformed into the diborane(6), (Eind)HB(μ-H)2BH(Eind) (4), with treatment with Me3SiCl. The Eind-based lithium trihydroaluminate [Li(OEt2)]2[(Eind)AlH3]2 (5) has been synthesized by the reaction of (Eind)Li with LiAlH4 in Et2O. The subsequent addition of Me3SiCl to a solution of 5 in toluene produced the dialumane(6), (Eind)HAl(μ-H)2AlH(Eind) (6), the heavier congener of 4. The dialumane(6) 6 reacted with lithium metal in a mixed solvent of Et2O and toluene to give the diarylalumane, (Eind)2AlH (7), via a disproportionation reaction along with the cleavage and recombination of the Al–C bond. The discrete monomeric structures of 1, 2, and 7 and dimeric structures of 3, 4, 5, and 6 have been determined by X-ray crystallography.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.6b00633.

    • NMR spectra of the compounds 2, 3, 5, and 7 (PDF)

    • Crystallographic details for 1, 2, 3, 4 (form I), 4 (form II) 5, 6, and 7 (CIF)

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