A. Nagasawa, Hideaki Tanaka, Masayuki Miyoshi
Dec 1, 1987
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Influential Citations
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Journal
Inorganic Chemistry
Abstract
The ligand exchange of cis-bis(acetylacetonato)dioxomolybdenum(VI) in acetylacetone has been studied kinetically with the /sup 14/C-labeling technique. The rate law was rate = (k/sub 1/ + k/sub 2/(H/sub 2/O))(complex) at 5.0, 15.0, 25.0, and 35.0/sup 0/C; k/sub 1/ and k/sub 2/ are 1.05 x 10/sup -3/ s/sup -1/ and 8.27 x 10/sup -3/ s/sup -1/ at 25/sup 0/C, respectively. ..delta..H* and ..delta..S* are 64 +/- 2 and 64 +/- 1 kJ mol/sup -1/ and -86 +/- 5 and -71 +/- 4 J K/sup -1/ mol/sup -1/ for k/sub 1/ and k/sub 2/, respectively. Dilution of the solvent with acetonitrile and deuteriation of the acidic hydrogens of the solvent and of water decreased both rate constants. Application of pressure to the solution up to 92 MPa at 5/sup 0/C caused no significant change in the rate law, and the rates themselves, i.e. ..delta..V double dagger s, were ca. 0 cm/sup 3/ mol/sup -1/. The mechanism of the reaction in discussed on the basis of these data.