Phenalenyl-based ligand for transition metal chemistry: Application in Henry reaction

Arup Mukherjee,Alexander Döring,Swadhin K Mandal,Carola Schulzke,Daniel Kratzert,Dietmar Stalke,Tamal K Sen

doi:10.1007/s12039-011-0107-2

Abstract

We report the synthesis and characterization of the first transition metal complex of a phenalenyl-based ligand. The reaction of Cu(OAc)2.H2O with 9-N-methylamino-1-N ′-methylimino-phenalene (LH) in 1:1 stoichiometric ratio results in the formation of a mononuclear copper complex [LCu(OAc)] (1). The molecular structure of 1 was established by X-ray crystallography. The electrochemistry of 1 indicates the formation of an anionic radical by one electron reduction into the non-bonding molecular orbital of the phenalenyl system. The complex 1 efficiently catalyses the C–C bond forming Henry reaction.

Highlights

The chemistry of phenalenyl-based ligand systems has not yet been explored except on the development of neutral boron containing free radical conductors.1,2 Phenalenyl is well-known odd alternant hydrocarbon with high symmetry (D3h) which has the ability to form three redox species: cation, radical, and anion.3 The formation of this redox triad involves the use of the nonbonding molecular orbital (MO) of the phenalenyl moiety and does not affect the stability of the resulting species greatly
We have synthesized and characterized the first transition metal complex of a phenalenyl-based ligand to be utilized as catalyst for carrying out Henry reaction
This result establishes that the phenalenylbased ligands can be used for the development of transition metal chemistry to design catalyst for homogeneous organic transformation

Summary

Introduction

The chemistry of phenalenyl-based ligand systems has not yet been explored except on the development of neutral boron containing free radical conductors. Phenalenyl is well-known odd alternant hydrocarbon with high symmetry (D3h) which has the ability to form three redox species: cation, radical, and anion. The formation of this redox triad involves the use of the nonbonding molecular orbital (MO) of the phenalenyl moiety and does not affect the stability of the resulting species greatly. Phenalenyl is well-known odd alternant hydrocarbon with high symmetry (D3h) which has the ability to form three redox species: cation, radical, and anion.3 The formation of this redox triad involves the use of the nonbonding molecular orbital (MO) of the phenalenyl moiety and does not affect the stability of the resulting species greatly. The neutral radical state is stabilized by the extended electronic delocalization and this way a number of phenalenyl-based organic conductors (chart 1) have been reported exhibiting the highest room temperature conductivity among any neutral radical solids.. The neutral radical state is stabilized by the extended electronic delocalization and this way a number of phenalenyl-based organic conductors (chart 1) have been reported exhibiting the highest room temperature conductivity among any neutral radical solids.1,2 Such characteristic features have been widely utilized for exploring new conjugated electronic systems, such as multifunctional electronic and magnetic materials..

Methods

Results

Conclusion