Theoretical characterization of molecular complexes formed between triplet vinyl nitrene and Lewis acids

• Type: Article in International Scientific Journal
• Date: 2015

Authors

Dario J R Duarte (Author) Other; Margarida S Miranda (Author) Other; Joaquim C G E Esteves da Silva (Author) FCUP

Journal

Title: Structural Chemistry

Vol. 26

Pages: 565-571

ISSN: 1040-0400

Publisher: Springer Nature

Indexing

ISI Web of Knowledge - 3 Citations

Scopus - 3 Citations

Scientific classification

FOS: Natural sciences > Chemical sciences

Other information

Authenticus ID: P-00A-9WF

DOI: 10.1007/s11224-014-0519-y

Abstract (EN): In the current work, the complexes formed between triplet vinyl nitrene ((CH2CHN)-C-3) and some Lewis acids YA (LiH, LiF, BeH2, BeF2, BH3, BF3, ClH, ClF, HCl, HF) have been investigated through calculations of the electronic structure. These calculations have been carried out in order to determine the energetic stability of the N center dot center dot center dot Y (with Y = Li, Be, B, Cl, H) interactions and also to understand their chemical nature. Quantum chemical calculations predict that the molecular complexes (CH2CHN)-C-3 center dot center dot center dot Y-A are always more stable than the separated (CH2CHN)-C-3 and Y-A species. The interaction energies range from -0.98 kcal mol(-1) (in CH2=CHN center dot center dot center dot ClH) to -39.03 kcal mol(-1) (in CH2=CHN center dot center dot center dot BH3) at the CCSD(T)/6-311++G(2d,2p) level of theory. Accordingly, some of these complexes may serve to experimentally detect and characterize the elusive triplet vinyl nitrene species. Moreover, AIM theory, in particular the L(r) = -A1/4a double dagger(2) rho(r) function, reveals that the N center dot center dot center dot Y interactions established between the electron lone pair of the nitrogen atom and the charge density depletion region of the Y atom are mainly of electrostatic character.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 7