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Calorimetric investigation of the reaction of 1,5-cyclooctadiene with complexes of the type (acac)M(olefin)2 [M = Rh(I), Ir(I)] |
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| Authors: | A.C. Jesse E.H.P. Cordfunke W. Ouweltjes |
| Affiliation: | Anorganisch Chemisch Laboratorium, J. H. van't Hoff Instituut, University of Amsterdam, Nieuwe Achtergracht 166, Amsterdam The Netherlands Netherlands Energy Research Foundation E.C.N., Petten The Netherlands |
| Abstract: | The enthalpies of reaction of the complexes (acac)M(olefin)2 (acac=acetyl-acetonate, M=Rh(I), Ir(I); olefin=ethylene, propene, vinyl chloride, vinyl acetate, methyl acrylate and styrene) with 1,5-cyclooctadiene in n-heptane, according to the reaction [(acac)M(olefin)2 + 1,5COD → (acac)M(1,5COD) + 2 olefin]n.heptane have been determined by solution calorimetry. From these results the influence of substituent R in the olefin CH2CHR on the M---(CH2CHR) displacement enthalpy has been derived. It is concluded that π back-bonding is slightly more important in the Ir---olefin bond than in the Rh---olefin bond. Furthermore, the data show that, as a result of steric factors which inhibit the approach of solvent molecules, solvation enthalpies are not additive. |
| Keywords: | To whom correspondence should be addressed. |
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