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Ligand isotopic exchange of cis-bis(acetylacetonato)dioxomolybdenum(VI) in acetylacetone

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00271a015· OSTI ID:5485608
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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.

Research Organization:
Tohoku Univ., Sendai, Japan
OSTI ID:
5485608
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:24; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
400701* -- Radiochemistry & Nuclear Chemistry-- Hot-Atom Chemistry
ACETYLACETONE
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CARBON 14
CARBON ISOTOPES
CHELATING AGENTS
CHEMICAL REACTION KINETICS
COMPLEXES
DATA
EVEN-EVEN NUCLEI
EXPERIMENTAL DATA
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
ISOTOPIC EXCHANGE
KETONES
KINETICS
LABELLING
LIGANDS
LIGHT NUCLEI
MOLYBDENUM COMPLEXES
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
PRESSURE DEPENDENCE
RADIOISOTOPES
REACTION KINETICS
REAGENTS
TRANSITION ELEMENT COMPLEXES
YEARS LIVING RADIOISOTOPES