Kinetic studies on the dimerization of molybdenum(V) in acid media and the crystal structure of K[MoOCl4(OH2)] · H2O |
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Authors: | Chang -Su Kim R Kent Murmann E O Schlemper |
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Affiliation: | (1) Department of Chemistry, University of Missouri, Schlundt Hall, 65201 Columbia, Missouri, USA |
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Abstract: | Summary MoOCl5]2– aquates rapidly in solutions ofca. 5 M or less in HCl or MeSO3H to give an intermediate which changes to the well known ion, Mo2O
4aq
2+
at a lower rate. Solutions of molybdenum(V) in 12M MeSO3H, when diluted, also change at a similar rate to Mo2O
4
2+
. The rate of reaction, dMo2O
4
2+
]/ dt=kMoV] has a value of k=30.(1)s–1 at 0°C in 5.00 MMeSO3H. At constant ionic strength, k is nearly independent of acidity (5.2–0.5 M) and is only slightly affected by exchanging MeSO
3
–
with Cl– orp-toluenesulfonate ion. At low ionic strength k increases dramatically. In 4.78 MMeSO3H, the activation parameters are: H=72.68(29) kJ/mole, S=16.63(8) jmole · K and k=5.01(5)×102s–1 at 0°C.18O measurements on the oxygen transfer between MoO
aq
3+
and Mo2O
4aq.
2+
were partially inconclusive. A mechanistic interpretation is given to the kinetic results. The x-ray crystal structure of KMoOCl4(OH2)·H2O is reported.On leave from Daegu University, Daegu, Korea. |
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Keywords: | |
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