Prototropic mu-H-8,H-9 and mu-H-9,H-10 Tautomers Derived from the [nido-5,6-C2B8H11](-) Anion

Tok, Oleg L.; Růžičková, Z.; Růžička, A.; Hnyk, Drahomír; Štíbr, Bohumil

doi:https://dx.doi.org/10.1021/acs.inorgchem.6b02076

Number of the records: 1

Prototropic mu-H-8,H-9 and mu-H-9,H-10 Tautomers Derived from the [nido-5,6-C2B8H11](-) Anion

1.

SYSNO ASEP	0466309
Document Type	J - Journal Article
R&D Document Type	Journal Article
Subsidiary J	Článek ve WOS
Title	Prototropic mu-H-8,H-9 and mu-H-9,H-10 Tautomers Derived from the [nido-5,6-C2B8H11](-) Anion
Author(s)	Tok, Oleg L. (UACH-T)_{RID, ORCID, SAI} Růžičková, Z. (CZ) Růžička, A. (CZ) Hnyk, Drahomír (UACH-T)_{SAI, RID, ORCID} Štíbr, Bohumil (UACH-T)_{RID, SAI, ORCID}
Number of authors	5
Source Title	Inorganic Chemistry. - : American Chemical Society - ISSN 0020-1669 Roč. 55, č. 20 (2016), s. 10122-10124
Number of pages	3 s.
Language	eng - English
Country	US - United States
Keywords	tautomers
Subject RIV	CA - Inorganic Chemistry
R&D Projects	GA16-01618S GA ČR - Czech Science Foundation (CSF)
Institutional support	UACH-T - RVO:61388980
UT WOS	000385785700024
EID SCOPUS	84992130154
DOI	https://doi.org/10.1021/acs.inorgchem.6b02076
Annotation	Reported is an unusual tautomeric behavior within the [nido-5,6-C2B8H11](-) (1a(-)) cage that has no precedence in the whole area of carborane chemistry. Isolated were two skeletal tautomers, anions [6-Ph-nido-5,6-C2B8H10-mu(8,9)](-) (2d(-)) and [5,6-Me-2-nido-5,6-C2B8H9-mu(9,10)](-) (3b(-)), which differ in the positioning of the open face hydrogen bridge. Their structures have been determined by X-ray diffraction analyses. The 3b(-) structure is stabilized by intermolecular interaction involving Et3NH+ and B8-B9 and H8 atoms in the solid phase; however, its dissolution in CD3CN causes instant conversion to the more stable [5,6-Me-2-nido-5,6-C2B8H9-mu(8,9)](-) (2b(-)) tautomer. The dynamic electron-correlation-based MP2/6-31G* computations suggest that the parent [nido-5,6-C2B8H11-mu(8,9)](-) (2a(-)) tautomer is 3.9 kcal center dot mol(-1) more stable than the [nido-5,6-C2B8H11-mu(9,10)](-) (3a(-)) counterpart and the mu(8,9) structure 2(-) is therefore the most stable tautomeric form in the solution, as was also demonstrated by multinuclear (H-1, B-11, and C-13) NMR measurements on the whole series of C-substituted compounds.
Workplace	Institute of Inorganic Chemistry
Contact	Jana Kroneislová, krone@iic.cas.cz, Tel.: 311 236 931
Year of Publishing	2017

Number of the records: 1