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Borabenzene Derivatives. 29. Synthesis and Structural Diversity of Bis(boratabenzene)scandium Complexes. Structures of [ScCl(C5H5BMe)2]2, [ScCl(3,5-Me2C5H3BNMe2)2]2, and ScCl[3,5-Me2C5H3BN(SiMe3)2]21

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journal contribution
posted on 20.11.1999, 00:00 by Gerhard E. Herberich, Ulli Englert, Andreas Fischer, Jiahong Ni, Andreas Schmitz
The bis(boratabenzene)scandium complexes 35 are synthesized from solvent-free lithium boratabenzenes and ScCl3 in toluene (110 °C, 3 days). Complex [ScCl(C5H5BMe)2]2 (3) possesses a doubly chloro-bridged dinuclear structure with four facially coordinated boratabenzene ligands. Compound [ScCl(3,5-Me2C5H3BNMe2)2]2 (4) differs from 3 in that each scandium atom binds to one boratabenzene in an unprecedented N−B−C-2 coordination mode and facially to the second boratabenzene ligand; in solution 4 is fluxional, displaying only one type of boratabenzene ligand with effective lateral symmetry. Complex ScCl[3,5-Me2C5H3BN(SiMe3)2]2 (5) is mononuclear because of the bulkiness of its boratabenzene. Metalation of the 1,2,3,6-tetrahydroborinine 3-CH2-5-MeC5H5BNMe2 (9) affords the solvent-free boratabenzene Li(3,5-Me2C5H3BNMe2) (7). The mixture of 1,2- and 1,4-dihydroborines 3,5-Me2C5H4BNMe2 (10a,b) (accessible from 9 by isomerization) can be transformed into the solvent-free boratabenzene Li[3,5-Me2C5H3BN(SiMe3)2] (8) by (i) treatment with BCl3 to give the chloro derivatives 11a,b, (ii) subsequent amination with NH(SiMe3)2/NEt3, and (iii) metalation with LiN(SiMe3)2.

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