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Mononuclear palladium and heterodinuclear palladium–ruthenium complexes of semicarbazone ligands. Synthesis, characterization, and application in C–C cross-coupling reactions

Mononuclear palladium and heterodinuclear palladium–ruthenium complexes of semicarbazone ligands. Synthesis, characterization, and application in C–C cross-coupling reactions

Authors :
Dipravath Kumar Seth
Samaresh Bhattacharya
William S. Sheldrick
Heike Mayer-Figge
Michael G. B. Drew
Sarmistha Halder
Sayanti Datta
Source :
RSC Advances. 2:5254
Publication Year :
2012
Publisher :
Royal Society of Chemistry (RSC), 2012.

Abstract

Reaction of salicylaldehyde semicarbazone (L1), 2-hydroxyacetophenone semicarbazone (L2), and 2-hydroxynaphthaldehyde semicarbazone (L3) with [Pd(PPh3)2Cl2] in ethanol in the presence of a base (NEt3) affords a family of yellow complexes (1a, 1b and 1c, respectively). In these complexes the semicarbazone ligands are coordinated to palladium in a rather unusual tridentate ONN-mode, and a PPh3 also remains coordinated to the metal center. Crystal structures of the 1b and 1c complexes have been determined, and structure of 1a has been optimized by a DFT method. In these complexes two potential donor sites of the coordinated semicarbazone, viz. the hydrazinic nitrogen and carbonylic oxygen, remain unutilized. Further reaction of these palladium complexes (1a, 1b and 1c) with [Ru(PPh3)2(CO)2Cl2] yields a family of orange complexes (2a, 2b and 2c, respectively). In these heterodinuclear (Pd–Ru) complexes, the hydrazinic nitrogen (via dissociation of the N–H proton) and the carbonylic oxygen from the palladium-containing fragment bind to the ruthenium center by displacing a chloride and a carbonyl. Crystal structures of 2a and 2c have been determined, and the structure of 2b has been optimized by a DFT method. All the complexes show characteristic 1H NMR spectra and, intense absorptions in the visible and ultraviolet region. Cyclic voltammetry on all the complexes shows an irreversible oxidation of the coordinated semicarbazone within 0.86–0.93 V vs. SCE, and an irreversible reduction of the same ligand within −0.96 to −1.14 V vs. SCE. Both the mononuclear (1a, 1b and 1c) and heterodinuclear (2a, 2b and 2c) complexes are found to efficiently catalyze Suzuki, Heck and Sonogashira type C–C coupling reactions utilizing a variety of aryl bromides and aryl chlorides. The Pd–Ru complexes (2a, 2b and 2c) are found to be better catalysts than the Pd complexes (1a, 1b and 1c) for Suzuki and Heck coupling reactions.

Details

ISSN :
20462069
Volume :
2
Database :
OpenAIRE
Journal :
RSC Advances
Accession number :
edsair.doi...........b5db0b4e72af50b67b6c3ec2657f54b7
Full Text :
https://doi.org/10.1039/c2ra20105d