Theoretical investigations of the Ir-catalyzed direct borylation of B(3,6)–H of o-carborane: the actual catalyst, mechanism, and origin of regioselectivity

Abstract

The IrIII species is proved to be the actual catalyst. The electron-delocalized structure and the inductive effects of the carbon centers is account for the regioselectivity.

Mechanism and Substituent Effects of Benzene Arylation via a Phenyl Cation Strategy: A Density Functional Theory Study

“…In this study, density functional theory (DFT) [33] was used because it has been widely applied in mechanistic studies of catalytic reactions, and shown to be an effective approach for gaining better insight into the origin of various selectivities. [34][35][36][37][38][39][40][41][42] All calculations were performed using the Gaussian 09 program. [43] All geometric structures of the reactants, products, transition states, and intermediates, were optimized using the M06-2X [44][45] density functional combined with the 6-31G(d,p) [46][47] basis set (denoted as Level A).…”

“…In this study, density functional theory (DFT) was used because it has been widely applied in mechanistic studies of catalytic reactions, and shown to be an effective approach for gaining better insight into the origin of various selectivities . All calculations were performed using the Gaussian 09 program .…”

Degradation mechanism of tris(2-chloroethyl) phosphate (TCEP) as an emerging contaminant in advanced oxidation processes: A DFT modelling approach

“…Previously, DFT has been successful applied to study catalytic mechanism and selectivity of organic reactions (Bai et al 2018. The degradation of TCPP initiated by •OH revealed by DFT that the HAP mechanism is most favorable as water provided a negative role in the degradation by modifying the stabilities of prereactive complexes via forming hydrogen bonds (Li et al 2017).…”

“…The DIE analysis proposed by Legault et al is an effective approach to unravel how the reaction barrier comes about (Legault et al 2007). It has been widely used in mechanism and origin of stereoselectivities studies of various organic and catalytic reactions (Bai et al 2018, Chai and Head-Gordon 2008, Wen et al 2015. The key process was to decompose the activation energy of the concerned transition state into to two main components: the distortion energy (ΔE ≠ dist) and interaction energy (ΔE ≠ int), as shown in Eq.…”

Regioselectivity of Pd-catalyzedo-carborane arylation: a theoretical view

“…[1][2][3] Since the 1960s, the precursor works and the definition for this kind of compound have been reported. 4 Meanwhile, the icosahedral carboranes as the most important carboranes have attracted widespread attention due to their many attractive properties, such as unique thermal and chemical stability, 5,6 enriched boron content, [7][8][9] three-dimensional aromaticity 10,11 and so on. [12][13][14] These characteristics make carboranes useful basic units in boron neutron capture therapeutics, [15][16][17][18][19] supramolecular design materials, [20][21][22][23][24][25][26][27][28][29][30] and coordination/organometallic chemistry.…”