ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
High-pressure 1H-NMR. has been used to determine volumes of activation (ΔV#) for solvent exchange with [M(S)6]3+ ion (M = Al(III), Ga(III); S = dimethylsulfoxide (DMSO) and N,N-dimethylformamide (DMF)) in [2H]3-nitromethane solution. For Al(III),Δ V# = + 15.6 ± 1.4 (S = DMSO, 358.5 K) and ΔV# = + 13.7 ± 1.2 cm3mol-1 (S = DMF, 354.5 K), whilst for Ga(III), ΔV# = + 13.1 ± 1.0 (S = DMSO, 334.6 K) and ΔV# = +7.9 ± 1.6 cm3mol-1 (S= DMF, 313.8 K). Variable temperature studies over a temperature range of 107.2 K (Al(III)) and 101.1 K (Ga(III)) were carried out for solvent exchange with [M(DMF)6]3+ ions in [2H]3-nitromethane solution, using stopped-flow NMR, and conventional linebroadening, and gave ΔH# = 88.3 ± 0.9 and 85.1 ± 0.6 kJ+ mol-1, and ΔS# = 28.4 ± 2.7 and 45.1 ± 1.9 JK-1 mol-1 for Al(III) and Ga(III) ions respectively. All of these results are consistent with dissociative modes of activation.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19800630127
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