NDLI: Theoretical study on homolytic C(sp<sup>2</sup>)

Content Provider	Royal Society of Chemistry (RSC)
Author	Wang, Yingxing Ding, Lanlan Zheng, Wenrui
Copyright Year	2015
Abstract	The C–O homolytic bond dissociation enthalpies (BDEs) of many ethers were calculated by high-level ab initio methods including G4, G3, CBS-Q, CBS-4M as well as 26 density function theory (DFT) methods. Among the DFT methods, wB97 provided the most accurate results and the root mean square error (RMSE) is 9.3 kJ mol−1 for 72 C–O BDE calculations. Therefore, extensive C(sp2)–O BDEs and the substituent effect of alkenyl ethers, para-position phenyl ethers/phenols as well as several typical heterocyclic ethers were investigated in detail by wB97 methods, which is important for the understanding of the chemical process involved in the cross-coupling reactions. For alkenyl ethers, the different substituents exhibited significant effects on C(sp2)–O BDEs, especially, the conjugate effect of the substituents on the O atom can greatly decrease the C(sp2)–O BDEs. In addition, the NBO analysis produced good linear correlations between the C(sp2)–O BDEs and qC × qO values (the qC and qO values denoted the natural charge of C and O atoms of the C–O bond, respectively). For para-position phenyl ethers and phenols, excellent linear relationships between the C(sp2)–O BDEs with substituent constant σp+ are found. Further discussion of the substituent effect separated into the ground effect and the radical effect can further help us to understand the essence. For several five-membered typical heterocyclic ethers, a larger bond angle change will lead to a smaller C–O BDE.
Starting Page	6935
Ending Page	6943
Page Count	9
File Format	HTM / HTML PDF
ISSN	11440546
Volume Number	39
Issue Number	9
Journal	New Journal of Chemistry
DOI	10.1039/c5nj01354b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Borland Database Engine Chemical bond CBS NBO Dissociative Substituent Phenyl group Power Mac G4 Heterocyclic compound Ab initio quantum chemistry methods Molecular geometry
Content Type	Text
Resource Type	Article
Subject	Chemistry Materials Chemistry Catalysis

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