Binding Selectivity Between Diazobenzene and Different Nucleophilic Reagents： Covalent and Noncovalent Interactions

doi:10.7503/cjcu20210237

Abstract

Abstract:

The specific interaction and reaction mechanism between aromatic diazonium salts and nucleophi-lic reagents have not been fully clarified yet. Within the framework of density functional theory， we calculated the binding sites and reaction coordinates of six different nucleophiles with diazobenzene. Chemical hardness of the attacking atom is the main descriptor for describing the binding site. Moreover， a quantitative descriptor is proposed to predict the activation energy barrier in terms of local ionization energy and charge distribution. These results are useful to gain insight for understanding the reaction mechanism of reactions involving aroma-tic diazonium salts and to explore better reaction conditions.

Key words: Diazobenzene, Spatial selectivity, Descriptor, Chemical hardness

CLC Number:

O641

TrendMD:

WANG Gaobo, MA Jing. Binding Selectivity Between Diazobenzene and Different Nucleophilic Reagents： Covalent and Noncovalent Interactions[J]. Chem. J. Chinese Universities, 2021, 42(7): 2238.

Figures/Tables 9

Fig.1 Schematic illustration of the reaction between diazobenzene and various nucleophiles(A), the proposal of cis and trans preference(B) and different binding modes(C)

Fig.2 ESP fitting surface(BWR colored, midpoint=0.77)(A) and atomic serial numbers(B) of diazobenzene

Table 1 Hirshfeld charges(q), global softness(S), and local softness for electrophilic(s-) and nucleophilic(s+) reactions for diazobenzene

Atom	Hirshfeld charge			Global softness S	Local softness
Atom	q（N-1）	q（N）	q（N+1）	Global softness S	s^-	s⁺
C1	0.070	0.016	-0.064	5.609	0.304	0.450
C2	0.207	0.072	0.032		0.754	0.227
C3	0.070	0.016	-0.064		0.304	0.450
C4	0.103	-0.004	-0.046		0.602	0.239
C5	0.213	0.020	-0.078		1.086	0.548
C6	0.103	-0.004	-0.046		0.602	0.239
H7	0.127	0.096	0.062		0.174	0.190
H8	0.127	0.096	0.062		0.174	0.190
H9	0.123	0.080	0.057		0.240	0.129
H10	0.140	0.081	0.042		0.332	0.215
H11	0.123	0.080	0.057		0.240	0.129
N12	0.310	0.269	0.098		0.230	0.957
N13	0.283	0.182	-0.111		0.567	1.644

Fig.3 Binding modes of diazobenzene with five different nucleophiles(A) PhN2BF4; (B) PhN2Cl; (C) PhN2OH; (D) PhN2OMe; (E) PhN2CN.

Fig.4 RDG scatter and isosurface plot of diazobenzene tetrafluoroborate

Fig.5 Decomposition process of diazobenzene with the help of tetrafluoroborate

Fig.6 Intrinsic reaction coordinate plots of the reactions for CN?(A) and SCN?attacking(called ATK in short, B) diazobenzene

Fig.7 RDG isosurface of the transition state attacked by thiocyanate with nitrogen atom

Fig.8 Relationship between the activation energy barrier, ΔE, and STC(Pearson’s r=0.99413)The red and blue circles represent trans and cis reaction paths, respectively.

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