Accurate ring strain energy calculations on saturated three-membered heterocycles with one group 13–16 element

Rey Planells, Alicia; Espinosa Ferao, Arturo

Publication:
Accurate ring strain energy calculations on saturated three-membered heterocycles with one group 13–16 element

dc.contributor.author	Rey Planells, Alicia
dc.contributor.author	Espinosa Ferao, Arturo
dc.contributor.department	Química Orgánica
dc.date.accessioned	2025-03-12T07:02:39Z
dc.date.available	2025-03-12T07:02:39Z
dc.date.issued	2020-08-17
dc.description	© 2020 American Chemical Society. This document is the Published Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.0c01316	es
dc.description.abstract	Accurate ring strain energy (RSE) data for parent (CH2)2X rings are reported, where X are group 13–16 elements (El) in their lowest oxidation state, from the second to the sixth row, with their covalence completed by bonds to H. They are obtained from appropriate homodesmotic and hyper-homodesmotic reactions at different levels up to the CCSD(T) level, thus providing a benchmark of high-quality reference RSE values, as well as acceptably accurate faster lower-level options. Derivatives of indium, thallium, and lead cannot be properly described by a three-member ring connectivity, because they display a unique donor–acceptor structure from an ethylene π(C═C) orbital to an empty p orbital of a metallylene subunit. The RSE of groups 13 and 14 heterocycles increases on descending in the group (except for Ga and Ge), while it decreases for groups 15 and 16. The latter is presumably due to a strain-releasing mechanism favored by the increase of p-character at the sp3-type atomic orbital used by El in the endocyclic El–C bonds, %p(El)El-C, originated by the tendency of the El lone pairs in groups 15–16 to increase their s-character. This strain-releasing mechanism does not exist in heavier tetrels, which keep almost unchanged the p-character in the endocyclic bonds at El, whereas for triels the p-character is still lower owing to their sp2-like hybridization. Remarkable linear correlations were found between the RSE and either the above-mentioned %p(El)El-C, the distal C–C bond distance or the relaxed force constants for the endocyclic bond angles.	es
dc.format	application/pdf	es
dc.format.extent	11	es
dc.identifier.citation	Inorganic Chemistry, 2020, Vol. 59, Issue 16, pp. 11503-11513
dc.identifier.doi	https://doi.org/10.1021/acs.inorgchem.0c01316
dc.identifier.issn	Print: 0020-1669
dc.identifier.issn	Electronic: 1520-510X
dc.identifier.uri	http://hdl.handle.net/10201/151571
dc.language	eng	es
dc.publisher	American Chemical Society	es
dc.relation	Sin financiación externa a la Universidad	es
dc.relation.publisherversion	https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c01316	es
dc.rights.accessRights	info:eu-repo/semantics/restrictedAccess
dc.subject	Chemical structure Elements Energy Heterocyclic compounds Hydrocarbons	es
dc.subject	Elements	es
dc.subject	Energy	es
dc.subject	Heterocyclic compounds	es
dc.subject	Hydrocarbons	es
dc.title	Accurate ring strain energy calculations on saturated three-membered heterocycles with one group 13–16 element	es
dc.type	info:eu-repo/semantics/article	es
dspace.entity.type	Publication	es