Solvation structure of magnesium, zinc, and alkaline earth metal ions in N,N‐dimethylformamide, N,N‐dimethylacetamide, and their mixtures studied by means of Raman spectroscopy and DFT calculations—Ionic size and electronic effects on steric congestion

Abstract

AbstractThe solvation structure of magnesium, zinc(II), and alkaline earth metal ions in N,N‐dimethylformamide (DMF) and N,N‐dimethylacetamide (DMA), and their mixtures has been studied by means of Raman spectroscopy and DFT calculations. The solvation number is revealed to be 6, 7, 8, and 8 for Mg2+, Ca2+, Sr2+, and Ba2+, respectively, in both DMF and DMA. The δ (OCN) vibration of DMF shifts to a higher wavenumber upon binding to the metal ions and the shift Δν(= νbound − νfree) becomes larger, when the ionic radius of the metal ion becomes smaller. The ν (NCH3) vibration of DMA also shifts to a higher wavenumber upon binding to the metal ions. However, the shift Δν saturates for small ions, as well as the transition‐metal (II) ions, implying that steric congestion among solvent molecules takes place in the coordination sphere. It is also indicated that, despite the magnesium ion having practically the same ionic radius as the zinc(II) ion of six‐coordination, their solvation numbers in DMA are significantly different. DFT calculations for these metalsolvate clusters of varying solvation numbers revealed that not only solvent–solvent interaction through space but also the bonding nature of the metal ion plays an essential role in the steric congestion. The individual solvation number and the Raman shift Δν in DMF–DMA mixtures indicate that steric congestion is significant for the magnesium ion, but not appreciable for calcium, strontium, and barium ions, despite the solvation number of these metal ions being large. Copyright © 2006 John Wiley & Sons, Ltd.