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Issue 39, 2009
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Enthalpy of ligand substitution in cisorganopalladium 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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Supplementary files

Article information


Submitted
22 May 2009
Accepted
29 Jul 2009
First published
27 Aug 2009

Dalton Trans., 2009, 8413-8420
Article type
Paper

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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