title: Relative energies of alpha and beta isomers of Keggin dodecatungstogallate.
abstract: The relative energies of beta Keggin heteropolytungstates, X(n+) W12O40(8-n)-, decrease as X(n+) is varied within period 3, from P5+ to Si4+ to Al3+. With heating of alpha-H5Ga3+ W12O40 at 200 degrees C in water, an equilibrated mixture of alpha (T(d); one 183W NMR signal) and beta (C(3v); three signals; 1:2:1 ratio) isomers is obtained. From deltaG(exp) = -RT ln K(beta-->alpha), in which (from 71Ga NMR spectra) K(beta-->alpha) (= [alpha]/[beta]) = 5.0, beta-GaW12O40(5-) is 0.65 kcal mol(-1) higher in energy than alpha-GaW12O40(5-). This finding is evaluated by analysis of the X-ray crystal structure alpha-K2Na3[GaW12O40] x 9.3 H2O [trigonal, space group P3(2)21, a = 18.9201(13) A, b = 18.9201(13) A, c = 12.5108(12) A, Z = 3, T = 100(2)K], comparison of the Shannon and Prewitt radii and Pauling electronegativities of Al3+ and Ga3+, and insight from density functional theory calculations, which predicted Ebeta - Ealpha = 0.32 kcal mol(-1).
authors.affiliation: Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
authors.forename: Karthik M
authors.initials: KM
authors.lastname: Sundaram
authors.forename: Wade A
authors.initials: WA
authors.lastname: Neiwert
authors.forename: Craig L
authors.initials: CL
authors.lastname: Hill
authors.forename: Ira A
authors.initials: IA
authors.lastname: Weinstock