Issue 7, 2002

One compound, two structures: synthesis, structures and reactivity of a novel (tripyrrinato)palladium(ii) trifluoracetate complex TrpyPdOAcf

Abstract

The novel (2,15-dimethyl-3,4,13,14-tetraethyltripyrrinato)palladium(II) trifluoroacetate (TrpyPdOAcf) 7 was found to exhibit two different geometries in the solid state. While in one crystal the tripyrrin ligand is helically distorted to ensure a square-planar coordination of the central palladium(II) ion, the bonding geometry of the metal centre of the other geometrical isomer found in a different crystal showed a pronounced tetrahedral deviation from planarity, accompanied with an almost planar tripyrrolic ligand. In solution, non-planar structures of 7 can not be detected, as judged by the results of variable temperature proton NMR spectroscopy. The energy stored in the strained complexes 6 and 7, however, becomes “visible” in fast ligand exchange processes, which enable us to prepare a number of new TrpyPdX complexes with X = Cl, Br, I, N3, NCO, SCN and OAc, of which the latter two decompose in solution. As the X-ray crystallographic analysis of TrpyPdBr 9 demonstrates, complexes with a tilted fourth ligand are predominant in the solid state with donor atoms larger than oxygen.

Graphical abstract: One compound, two structures: synthesis, structures and reactivity of a novel (tripyrrinato)palladium(ii) trifluoracetate complex TrpyPdOAcf

Supplementary files

Article information

Article type
Paper
Submitted
18 Oct 2001
Accepted
23 Jan 2002
First published
08 Mar 2002

J. Chem. Soc., Dalton Trans., 2002, 1391-1395

One compound, two structures: synthesis, structures and reactivity of a novel (tripyrrinato)palladium(II) trifluoracetate complex TrpyPdOAcf

M. Bröring and C. D. Brandt, J. Chem. Soc., Dalton Trans., 2002, 1391 DOI: 10.1039/B109510M

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