A computational analysis of the apparent nido vs. hypho conflict: are we dealing with six- or eight-vertex open-face diheteroboranes?

TY - JOUR

T1 - A computational analysis of the apparent nido vs. hypho conflict

T2 - are we dealing with six- or eight-vertex open-face diheteroboranes?

AU - Nunes, João Pedro F

AU - Holub, Josef

AU - Rankin, David W H

AU - Wann, Derek A

AU - Hnyk, Drahomír

N1 - Date of Acceptance: 02/06/2015. © Royal Society of Chemistry 2015. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details

PY - 2015/6/8

Y1 - 2015/6/8

N2 - A series of computational studies have been undertaken to investigate the electronic structures and bonding schemes for six hetero-substituted borane cages, all of which have been presented in the literature as potential hypho structures. The six species are hypho-7,8-[C2B6H13]- (1a), hypho-7,8-[CSB6H11]- (1b), hypho-7,8-[S2B6H9]- (1c), hypho-7,8-[NSB6H11] (1d), exo-7-Me-hypho-7,8-[NCB6H12] (1e), and endo-7-Me-hypho-7,8-[NCB6H12] (1f) and the so-called mno rule has been applied to each of them. As no structural data are known for the carbathia-, azathia-, and dithiahexaboranes, we have also applied the ab initio/GIAO/NMR structural tool for 1b-1d, with 1c having been prepared for this purpose. We conclude that an mno count of 10 means that 1a, 1b, 1d, 1e, and 1f should be termed pseudo-nido or pseudo-hypho. Only can be considered to be correctly termed hypho-7,8-[S2B6H9]-.

AB - A series of computational studies have been undertaken to investigate the electronic structures and bonding schemes for six hetero-substituted borane cages, all of which have been presented in the literature as potential hypho structures. The six species are hypho-7,8-[C2B6H13]- (1a), hypho-7,8-[CSB6H11]- (1b), hypho-7,8-[S2B6H9]- (1c), hypho-7,8-[NSB6H11] (1d), exo-7-Me-hypho-7,8-[NCB6H12] (1e), and endo-7-Me-hypho-7,8-[NCB6H12] (1f) and the so-called mno rule has been applied to each of them. As no structural data are known for the carbathia-, azathia-, and dithiahexaboranes, we have also applied the ab initio/GIAO/NMR structural tool for 1b-1d, with 1c having been prepared for this purpose. We conclude that an mno count of 10 means that 1a, 1b, 1d, 1e, and 1f should be termed pseudo-nido or pseudo-hypho. Only can be considered to be correctly termed hypho-7,8-[S2B6H9]-.

U2 - 10.1039/c5dt01460c

DO - 10.1039/c5dt01460c

M3 - Article

C2 - 26053287

SN - 1477-9234

VL - 44

SP - 11819

EP - 11826

JO - Dalton Transactions

JF - Dalton Transactions

ER -