om6b00633_si_002.cif (12.16 MB)

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

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posted on 26.09.2016, 16:40 by Takahiro Murosaki, Shohei Kaneda, Ryota Maruhashi, Kazuya Sadamori, Yoshiaki Shoji, Kohei Tamao, Daisuke Hashizume, Naoki Hayakawa, Tsukasa Matsuo
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.