Nuclear quadrupole resonance investigation of the comparative differences between hexachloro-stannate, -tellurate, and -plumbate resulting from cationic effects

Abstract

N.q.r. frequencies of 14 salts of SnCls2-, TeC162-, and PbC162-have been recorded in a n effort to observe possible differences in anion distortion which could result from the ' inert ' pair electrons of TeIV. There is no evidence of stereochemical activity of the TeIV ' inert ' pair as might be indicated by an increase in the number of chlorine resonance frequencies and/or anomalous changes in bond ionicity in any of the compounds studied. PbCIG2appears to be more sensitive to the cation than SnCls2-but the TeCIe2-ion is less sensitive. It is concluded that anion sensitivity to the cation is not readily predictable on the basis of the size alone.

Structural Phase Transitions and Ionic Motions in Pyridinium Hexachlorotellurate(IV),Hexachlorostannate(IV), and Hexabromostannate(IV) Crystals as Studied by 1H NMR

“…The crystals of (pyH)2TeCl6, (pyH)2SnCl6, and (pyH),SnBr6 were prepared according to the method described in [2,9] and purified by recrystallization from a hydrochloric or hydrobromic acid solution. The prepared samples were identified by conventional elementary analysis and by taking X-ray powder patterns, which were compared with those reported in [1,2,5], Results Figure 1 shows the temperature dependence of *H NMR M2 determined for the powdered samples of (pyH)2TeCl6, (pyH)2SnCl6, and (pyH)2SnBr6.…”

Proton NMR study of molecular dynamics and phase transitions in dimethylammonium hexachloro plumbate [NH2(CH3)2]2PbCl6

“…The second moment values, computed in ammonium halides using the above procedure, compare well with those reported (Gutowsky, Pake and Bersohn, 1954). Brill and Welsh (1973) report the preparation of the compound by the reaction of a solution of lead acetate in concentrated hydrochloric acid with a solution of dimethylammonium chloride in concentrated hydrochloric acid. They also report the crystallisation of the compound by slow cooling of the acid solution with continuous passage of chlorine gas.…”

Thermochemical bond energies and chlorine-35 nuclear quadrupole resonance spectra of hexachlorogermanate(2-), hexachlorostannate(2-), and hexachloroplumbate(2-) ions

“…36 The heat of solution of KCl(c) in 0.298 M HC1 is calculated in the following manner using data from Parker.31 Numbers preceding formulas indicate the number of moles. 0.0737HQ (in 13.39H20) + 0.00133KC1 (in 0.2417H2O)-> 0.00133KC1 [in 0.0737HC1 (in 13.63H20)] (9) 0.0737HC1 (in 13.63H,0) -* 0.0737HC1 (in 13.39H20) + 0.24 2 (10) 0.00133KCl(c) + 0.2417H2O -> 0.00133KC1 (in 0.2417H2O) (11) Adding reactions 9, 10, and 11 gives 0.00133KQ(c) + 0.0737HQ (in 13.63H2OH 0.00133KQ [in 0.0737 HQ (in 13.63H20)]…”