A Study of Solvent Electron-Pair Donor Ability and Lewis Basicity Scales.

Vibrational spectroscopic force field studies of dimethyl sulfoxide and hexakis(dimethyl sulfoxide)scandium(iii) iodide, and crystal and solution structure of the hexakis(dimethyl sulfoxide)scandium(iii) ion

“…17 O NMR chemical shifts, showing the interactions to be weaker for acetone. 7a, 8 Other, more noticeable changes take place for the S-O stretching vibrational mode, which has a more complex character. The S-O stretching frequency decreases substantially from gas to liquid for dimethyl sulfoxide (Tables 2, 3), and the corresponding force constant is reduced by almost 9% (Table 6).…”

An EXAFS Spectroscopic, Large‐Angle X‐Ray Scattering, and Crystallographic Study of Hexahydrated, Dimethyl Sulfoxide and Pyridine 1‐Oxide Hexasolvated Mercury(II) Ions

“…The configuration of monodentate ligands around mercury(II) is mostly dominated by linear, trigonal, and tetrahedral arrangements; six-coordinated complexes are few and often distorted. [1] The first apparently regular six-coordinated complex was reported for the solid hexakis(pyridine 1-oxide)mercury(II) perchlorate, [HgA C H T U N G T R E N N U N G (ONC 5 H 5 ) 6 ]A C H T U N G T R E N N U N G (ClO 4 ) 2 , with six equidistant Hg À O bonds at 2.35 (2) , which was determined crystallographically. [2] Subsequently, the crystal structures of other oxygen-donor ligands, that is, hexaaquamercury(II) perchlorate and hexakis(dimethyl sulfoxide)mercury(II) trifluoromethanesulfonate, also displayed solvated mercury(II) ions in sites with six equidistant Hg À O bonds at 2.341(6) and 2.347(5) , respectively.…”

“…[2] Subsequently, the crystal structures of other oxygen-donor ligands, that is, hexaaquamercury(II) perchlorate and hexakis(dimethyl sulfoxide)mercury(II) trifluoromethanesulfonate, also displayed solvated mercury(II) ions in sites with six equidistant Hg À O bonds at 2.341(6) and 2.347(5) , respectively. [3,4] For hexakis(dimethyl sulfoxide)mercury(II) perchlorate the octahedral coordination is slightly distorted with the two axial Hg À O bonds somewhat longer, 2 2.376 (6) , than the four equatorial ones, 2 2.317(6) and 2 2.320 (6) . [5] The tetragonal elongation of the octahedral configuration becomes more pronounced with the somewhat softer electron-pair donor pyridine [6] in hexakisA C H T U N G T R E N N U N G (pyridine)mercury (II) trifluoromethanesulfonate, with the equatorial and axial Hg À N distances within the ranges 2.402-2.442 and 2.497-2.499 , respectively.…”

Revisiting HgCl2: A solution- and solid-state 199Hg NMR and ZORA–DFT computational study

“…The resonance position of mercury in this solution is reported to be -1501.6 ppm. As HgCl 2 is a Lewis acid [10][11][12], its structure in electron-donating solvents may be expected to be different from that of the nearly linear Cl-Hg-Cl (bond angle of 178.9°) in the solid material [13], which may result in a chemical shift that is strongly dependent on concentration and/or temperature. The use of DMSO as a solvent in the present study, as opposed to alcohols or water, is meant to eliminate or minimize hydrogen bonding to the chlorine [14].…”