Concurrent NCS–substitution at non-equivalent molybdenum(IV) centres of the incomplete cuboidal aqua ion [Mo3(µ3-S)(µ-O)(µ-S)2(H2O)9]4+
- 1 January 1988
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 8,p. 2239-2240
- https://doi.org/10.1039/dt9880002239
Abstract
The kinetics of NCS– substitution on the unsymmetrical (crystallographically defined) molybdenum(IV) aqua ion, Mo3SOS2 4+, have been studied, under conditions in which substitution is confined to 1 : 1 reaction at each MoIV. Biphasic behaviour was observed with first Mo3SOS2 4+(> 10-fold) and then NCS–(> 10-fold) in excess, and two equilibration rate constants were obtained. These correspond to concurrent substitution at the molybdenum(IV) centres, two of one kind and one of another. A statistical factor of 2 applies to the slower process, which is therefore assigned to substitution at the two µ-oxo co-ordinated molybdenum(IV) centres. Formation rate constants are 82 and 23 M–1 s–1 respectively at 25 °C in 2 M HClO4.Keywords
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