Transformation of various multicenter bondings within bicapped-square antiprismatic motifs: Z-rearrangement

Bakardjiev, Mario; Holub, Josef; Růžičková, Z.; Růžička, A.; Fanfrlík, Jindřich; Štíbr, Bohumil; McKee, M.L.; Hnyk, Drahomír

doi:https://dx.doi.org/10.1039/d0dt04225k

Number of the records: 1

Transformation of various multicenter bondings within bicapped-square antiprismatic motifs: Z-rearrangement

1.

SYSNO ASEP	0543373
Document Type	J - Journal Article
R&D Document Type	Journal Article
Subsidiary J	Článek ve WOS
Title	Transformation of various multicenter bondings within bicapped-square antiprismatic motifs: Z-rearrangement
Author(s)	Bakardjiev, Mario (UACH-T)_{SAI, RID} Holub, Josef (UACH-T)_{SAI, RID, ORCID} Růžičková, Z. (CZ) Růžička, A. (CZ) Fanfrlík, Jindřich (UOCHB-X)_{RID, ORCID} Štíbr, Bohumil (UACH-T)_{RID, SAI, ORCID} McKee, M.L. (US) Hnyk, Drahomír (UACH-T)_{SAI, RID, ORCID}
Source Title	Dalton Transactions. - : Royal Society of Chemistry - ISSN 1477-9226 Roč. 50, č. 35 (2021), s. 12098-12106
Number of pages	9 s.
Language	eng - English
Country	GB - United Kingdom
Keywords	Bond formation ; Molecular rearrangement ; Isomerization
Subject RIV	CA - Inorganic Chemistry
OECD category	Inorganic and nuclear chemistry
Subject RIV - cooperation	Institute of Organic Chemistry and Biochemistry - Physical ; Theoretical Chemistry
R&D Projects	GA19-17156S GA ČR - Czech Science Foundation (CSF)
Method of publishing	Limited access
Institutional support	UACH-T - RVO:61388980 ; UOCHB-X - RVO:61388963
UT WOS	000784262000001
EID SCOPUS	85113155998
DOI	10.1039/d0dt04225k
Annotation	Reported herein are mutual rearrangements in the whole series of seven bicapped-square antiprismatic closo-C2B8H10 by means of high-quality computations that disprove the earlier postulated dsd (diamond-square-diamond) scheme for these isomerizations. The experimentally existing closo-1,2-C2B8H10 was able to be converted to 1,6-, and 1,10-isomers by pyrolysis, and the dsd (diamond-square-diamond) mechanism was offered as an explanation of these processes. However, these computations disprove the postulated dsd scheme for these isomerizations that take place in the ten-vertex closo series. Experimentally observed thermal rearrangements, both in the parent and substituted closo-1,2-C2B8H10, closo-1-CB9H10−, and closo-B10H102−, indirectly support these refined computations. All these processes are based on the new concept of the so-called Z-mechanism, being consistent with a transition state of a boat shape with an open hexagonal belt that results from the initial breakage of three bonds. Such bond breakings and the consequent bond formations bring to mind the shape of the letter Z. In effect, the pattern of multicenter bonding shifts from reactant through a transition state to product. The molecular rearrangements that are available experimentally favour either the axial or equatorial isomers, and this ratio depends on temperature and the type of cluster and its substitution.
Workplace	Institute of Inorganic Chemistry
Contact	Jana Kroneislová, krone@iic.cas.cz, Tel.: 311 236 931
Year of Publishing	2022
Electronic address	https://pubs.rsc.org/en/content/articlelanding/2021/DT/D0DT04225K#!divAbstract

Number of the records: 1