Donor–Acceptor Complexes between Ammonia and Sulfur Trioxide: An FTIR and Computational Study

Abstract

The complexes of ammonia with sulfur trioxide have been studied using FTIR matrix isolation spectroscopy and DFT/B3LYP calculations with the aug-cc-pVTZ basis set. The NH3/SO3/Ar matrixes were prepared in two different ways. In one set of experiments the matrix was prepared by the simultaneous deposition of the NH3/Ar mixture and SO3 vapor from the thermal decomposition of K2S2O7. In the second set of experiments thermolysis products of sulfamic acid were trapped in an argon matrix. Both methods of matrix preparation led to the formation of the H3N·SO3 electron donor-acceptor complex that was characterized earlier. In the matrixes comprising thermolysis products of sulfamic acid, in addition to H3N·SO3, the H3N-SO3···NH3 complex (II(D)) was also identified. The identity of the complex was confirmed by comparison of the experimental and theoretical spectra of H3N-SO3···NH3 and D3N-SO3···ND3. The performed calculations show that in H3N-SO3···NH3 the two N atoms and the S atom are collinear; the two S-N bonds are nonequivalent, one is much shorter (2.230 Å) than the other one (2.852 Å). In the AIM topological analysis, the interaction energy decomposition and topological properties of the electron localizability indicator (ELI-D) allowed us to categorize the stronger N-S bond in the II(D) complex as a dative bond and to assume that the fragile N-S bond is a consequence of a weak electron-donor-acceptor interaction. The calculations indicate that the identified II(D) complex corresponds to a local minimum on the PES of the NH3/SO3 system of 2:1 stoichiometry. The (NH3)2SO3 complex, II(HB), corresponding to a global minimum is 7.95 kcal mol(-1) more stable than the II(D) complex. The reason that the II(D) complex is present in the matrix but not the II(HB) complex is discussed.

Nature of the Interaction of Pyridines with OCS. A Theoretical Investigation

“…These complexes involve the interaction of the XB...YZ type where Y possesses one or more electron pairs. They have been classified into halogen bonds where B is a halogen [5][6][7][8][9][10][11][12][13][14][15], chalcogen bonds where B = O, S, Se [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34], and more recently, tetrel bonds where B = C, Si [35][36][37][38][39][40][41][42]. These bonds are unusual in that they involve a close approach of two electronegative atoms such as Cl, O, C on the one hand, and Y atoms such as N on the other hand.…”

Cooperative effects between π-hole triel and π-hole chalcogen bonds

“…For instance, bidentate chalcogen bonding increases the association constant by an order of magnitude in binding of peruoroaryl-substituted tellurophenes with an anion. 19 Thus, substantial theoretical attention has been paid to the cooperative effect of chalcogen bonding with itself and other types of interactions, [26][27][28][29][30][31][32][33] showing some interesting results. For instance, although SO 3 /NH 3 /NH 3 is more stable than NH 3 -SO 3 /NH 3 , the latter is identied in argon matrixes, where the two N-S bonds are nonequivalent.…”

“…For instance, although SO 3 /NH 3 /NH 3 is more stable than NH 3 -SO 3 /NH 3 , the latter is identied in argon matrixes, where the two N-S bonds are nonequivalent. 33 A trivalent triel atom in TrR 3 , owing to its electron deciency, is usually used to bind with Lewis bases such as HCN, CH 3 CN, and NH 3 . [34][35][36][37][38][39][40][41] Upon complexation, the geometric structure of TrR 3 exhibits substantial deviation from the planar one, and it becomes more prominent for a stronger triel bond.…”

Nature of the interaction between ammonia derivatives and carbon disulfide. A theoretical investigation

“…They can form N···X halogen bonds with halogen or mixed halogens, CF 3 X, hypohalous acids, and ClX . NH 3 and its derivatives can also interact with ] or ] to form chalcogen bonds or with F 4‐ n H n P + to form pnicogen bonds . In contrast, only few results on the complexing ability of CS 2 are available in the literature.…”