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Issue 39, 2009
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Enthalpy of ligand substitution in cis organopalladium complexes with monodentate ligands

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Abstract

The enthalpy for the substitution reaction cis-[PdRf2(THF)2] + 2 L →cis-[PdRf2L2] + 2THF (THF = tetrahydrofuran) has been measured in THF by calorimetric methods for Rf = 3,5-dichloro-2,4,6-trifluorophenyl, L = PPh3, AsPh3, SbPh3, PMePh2, PCyPh2, PMe3, AsMePh2, or L2 = dppe (1,2-bis(diphenylphosphino)ethane), dppf (1,1′-bis(diphenylphosphino)ferrocene). The values determined show that the substitution enthalpy has a strong dependence on the electronic and steric properties of the ligand. The study of the consecutive substitution reactions cis-[PdRf2(THF)2] + L cis-[PdRf2L(THF)] + THF, and cis-[PdRf2L(THF)] + L →cis-[PdRf2L2] + THF has been carried our for L = PPh3 and L = PCyPh2. The first substitution is clearly more favorable for the bulkier leaving ligand, but the second gives practically the same ΔH value for both cases, indicating that the differences in steric hindrance happen to compensate the electronic differences for both ligands. The X-ray structures of cis-[PdRf2(PMePh2)2], cis-[PdRf2(dppe)] and cis-[PdRf2(dppf)] are reported.

Graphical abstract: Enthalpy of ligand substitution in cis organopalladium complexes with monodentate ligands

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Publication details

The article was received on 22 May 2009, accepted on 29 Jul 2009 and first published on 27 Aug 2009


Article type: Paper
DOI: 10.1039/B910055E
Citation: Dalton Trans., 2009, 8413-8420
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    Enthalpy of ligand substitution in cis organopalladium complexes with monodentate ligands

    G. Salas, J. A. Casares and P. Espinet, Dalton Trans., 2009, 8413
    DOI: 10.1039/B910055E

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