Benzene Forms Hydrogen Bonds with Water

Abstract

Fully rotationally resolved spectra of three isotopic species of 1:1 clusters of benzene with water (H(2)O, D(2)O, and HDO) were fit to yield moments of inertia that demonstrate unambiguously that water is positioned above the benzene plane in nearly free internal rotation with both hydrogen atoms pointing toward the pi cloud. Ab initio calculations (MP2 level of electron correlation and 6-31 G(**) basis set with basis set superposition error corrections) predict a binding energy D(e) greater, similar 1.78 kilocalories per mole. In both the experimental and theoretical structures, water is situated nearly 1 angstrom within the van der Waals contacts of the monomers, a clear manifestation of hydrogen bond formation in this simple model of aqueous-pi electron interactions.

A Systematic CCSD(T) Study of Long-Range and Noncovalent Interactions between Benzene and a Series of First- and Second-Row Hydrides and Rare Gas Atoms

“…For systems where the zero-point energy has also been accurately determined, the vibrationally averaged binding energy (D 0 ) is calculated and compared with experimental results. [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] For clarity, the results of all previous experimental and high-level ab initio studies on benzene-small molecule systems are summarized in Table 1.…”

Feet on the potential energy surface, head in the pi clouds

“…Two CH 3 -substituted dimers (3.7B,C) and the F-substituted dimer benzene-phenol is thus similar to that in the benzene-water dimer. 62 The important role of the hydroxyl group in the binding of benzene-phenol in the T-shaped isomer is also reflected in the modestly larger polarization term as compared to other dimers. Both conformations of the T-shaped-like benzene-toluene dimer are slightly stabilized by dispersion.…”

Multidentate carborane-containing Lewis acids and their chemistry: mercuracarborands

“…The oxygen to benzene distance of 2.99(1) Å is much shorter than either the spectroscopically (3.32Á/3.35 Å ) [33] or theoretically (3.20Á/3.32 Å ) [33,34] determined distances. This is the first solid-state structure of a benzene Á/water hydrogen bonded complex.…”