Issue 13, 2012

Novel saccharinate-bridged palladium complexes for efficient C–O bond activation displaying promising luminescence properties

Abstract

The synthesis of mono- and dinuclear cyclometallated palladium(II) complexes with deprotonated saccharinate ligands displaying different coordination modes is described. The new compounds were prepared by direct reaction between saccharine and the corresponding hydroxo-complexes [{Pd(μ-OH)(C⁁N)}2] (C^N = 2-(2-pyridyl)phenyl (Phpy) I; = 7,8-benzoquinolyl (Bzq) II), showing a general formula [{Pd(μ-sac)(C^N)}2] with saccharinate 1 displaying a bridging –NCO-coordination mode. Bridge splitting with neutral ligands (L = pyridine (py) 2, quinoline (quinol) 3 or acridine (acrid) 4) yielded new mononuclear derivatives with saccharinate acting as an N-monodentated ligand. Structural characterization by X-ray diffraction of complexes I1, I2 and II2 confirmed the proposed formulae. All complexes emit in the solution and solid state at room temperature. Emission features between 640–680 nm in the solid state for complexes I1 and II1 are significantly red-shifted if compared to the emission in solution. These broad emissions are consistent with the simultaneous presence of 3ππ* and 3MMLCT transitions indicating the existence of a strong intramolecular Pd–Pd ground state interaction. The dimeric complexes have also shown to catalyze Suzuki–Miyaura cross-coupling of coumaryl tosylate and aryl boronic acids under phosphine-free conditions. Initial studies suggest the involvement of palladium nanoparticles, which has been further investigated using mercury-drop test and poisoning experiments.

Graphical abstract: Novel saccharinate-bridged palladium complexes for efficient C–O bond activation displaying promising luminescence properties

Supplementary files

Article information

Article type
Paper
Submitted
15 Nov 2011
Accepted
18 Jan 2012
First published
24 Feb 2012

Dalton Trans., 2012,41, 3832-3842

Novel saccharinate-bridged palladium complexes for efficient C–O bond activation displaying promising luminescence properties

M. D. Santana, R. García-Bueno, G. García, G. Sánchez, J. García, A. R. Kapdi, M. Naik, S. Pednekar, J. Pérez, L. García, E. Pérez and J. L. Serrano, Dalton Trans., 2012, 41, 3832 DOI: 10.1039/C2DT12187E

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