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- W1480992409 abstract "Abstract The kinetics and mechanisms of intermolecular ligand exchange of acetylacetonate (acac) groups between “bulk” free acetylacetone (enol form) and R 2 Sn-(acac) 2 (R CH 3 or Ph) complexes have been re-investigated in chloroform- d (R CH3) and chlorobenzene (R Ph) solutions by proton magnetic resonance spectroscopy using the total lineshape analysis in the temperature range: 12.7–37.0°C (R CH 3 ;acac CHregion),−1.4 to 19.6°C (R CH 3 ; acac CH 3 region), and 25.9–48.0°C (R Ph; acac CHregion). The activation energies and entropies of activation are: for R CH 3 , 7.2 ± 0.7 kcal/mol and −30 ± 3 eu (acac CH 3 ), and 6.3 ± 0.6 kcal/mol and −32 ± 2 eu (acac CH); for R Ph 8.8 ± 2.7 kcal/mol and −31 ± 9 eu (acac CH). Concentration dependence studies for both the (CH 3 ) 2 Sn(acac) 2 Hacac and Ph 2 Sn(acac) 2 Hacac systems indicate that the rate of acetylacetonate exchange is first-order in the concentration of R 2 Sn(acac) 2 and zero order in the concentration of “bulk” free ligand. The intermolecular ligand exchange phenomenon is believed to involve coordination number lowering; viz. a Sn-O bond rupture as the rate-determining step to yield a five-coordinate intermediate species with a dangling unidentate acetylacetonate ligand." @default.
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- W1480992409 date "1977-03-01" @default.
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- W1480992409 title "]Kinetics and mechanisms of intermolecular ligand exchange" @default.
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- W1480992409 doi "https://doi.org/10.1016/s0022-328x(00)98065-3" @default.
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