Structures of arachno- and hypho-B(10) Clusters and Stability of Their Possible Lewis Base Adducts ([B(10)H(12)](2-), [B(10)H(12).L](2)(-), [B(10)H(12).2L](2)(-), [B(10)H(13)](-), [B(10)H(13).L](-), [B(10)H(12).2L]). An ab Initio/IGLO/NMR Investigation

Matthias Hofmann; Paul von Ragué Schleyer

doi:10.1021/ic9805729

Structures of arachno- and hypho-B(10) Clusters and Stability of Their Possible Lewis Base Adducts ([B(10)H(12)](2-), [B(10)H(12).L](2)(-), [B(10)H(12).2L](2)(-), [B(10)H(13)](-), [B(10)H(13).L](-), [B(10)H(12).2L]). An ab Initio/IGLO/NMR Investigation

Inorg Chem. 1998 Oct 19;37(21):5557-5565. doi: 10.1021/ic9805729.

Authors

Matthias Hofmann¹, Paul von Ragué Schleyer

Affiliation

¹ Center for Computational Quantum Chemistry, University of Georgia, 1004 Cedar Street, Athens, Georgia 30602-2525, and Computer-Chemie-Centrum, Institut für Organische Chemie, Universität Erlangen-Nürnberg, Henkestrasse 42, D-91052 Erlangen, Germany.

PMID: 11670702
DOI: 10.1021/ic9805729

Abstract

The [B(10)H(12)](2)(-) dianion has been shown by the ab initio/IGLO/NMR method to have a C(2) symmetric structure (26) derived from B(10)H(14) (17) by removing two opposite bridge protons. Adduct formation with one or two solvent molecules, suggested on the basis of experimental NMR investigations, does not take place. [B(10)H(12).nL](2)(-) (n = 1, 2) structures with various ligands are not bound (vs [B(10)H(12)](2)(-) and n L) and do not reproduce the experimental (11)B NMR chemical shifts. The [B(10)H(13)](-) structure (19), computed to have C(1) rather than C(s)() symmetry in solution (as in the solid state), also can be derived from B(10)H(14) (17) by removal of a bridging proton. In both the mono- (19) and the dianion (26), a bridging hydrogen can rearrange easily from B5/B6 to B9/B10 (barrier ca. 5 kcal mol(-)(1)) but not from B8/B9 to B9/B10 (barrier ca. 15 kcal mol(-)(1)). The recently proposed 6,6-(C(5)H(5)N)(2)B(10)H(12) structure is not supported computationally.