Project title

Enhancing synergistic effect for oxidative cross coupling using heterogeneous binuclear [CuIILnIII] catalysts

Project acronym

HBSynCat

Project Code and number

PN-III-P1-1.1-PD-2016-1054, Nr. 29/2018

Contracting Authority

UEFISCDI,

Project Host Institution

University of Bucharest

Run period

02.05.2018-30.04.2020

Total funding

250.000,00 lei


Project Summary

 

In view of the need to develop new environmentally friendly catalytic materials with tunable properties, the project proposal offers the possibility of developing new heterogeneous catalytic system with enhanced synergistic effect, in order to easy achieve the most demanded catalytic reactions - oxidative cross coupling.

The main objective represents the synthesis of new heterogeneous Schiff-base based binuclear [CuIILnIII] catalysts by immobilization of homogeneous heterobimetallic Cu/La(OTf)3 complex on graphene-based support. Different immobilization approaches will be used to find the most efficient one by correlating catalytic results with methodology of catalytic synthesis. To reach this goal, the project proposal is based on the achievement of the following objectives:

 

The implementation degree of the project:

 

Phase I/2018 (02.05.2018 - 31.12.2018): Synthesis and functionalization of binuclear [CuIILnIII] complexes with compartmental ligands.

Activity 1.1.  Synthesis and functionalization of binuclear homogeneous catalysts [CuIILnIII] with Schiff-base ligands;

Activity 1.2.  Functionalization of binuclear [CuIILnIII] complexes;

 

Summary of the research report (Phase I):

 In the first phase of the project, comprised between May 2018 and December 2018, all proposed tasks were achieved. A series of heterobinuclear complexes [CuII(Ln)LaIII] were synthesized and preliminarily characterized by DRIFT, powder XRD and UV-Vis. The catalytic materials obtained were tested in the oxidative coupling reaction of indole with methyl-vinyl-ketone. The reaction conditions were optimized and the results of the catalytic performance correlated with the method of synthesis of the complexes. The highest achieved yield was 91.4%. The first functionalized and subsequently immobilized complex on graphene oxide was performed by reaction between the hydroxyl group of amine from the Schiff base of the ligand and the epoxide groups on the surface of the graphene oxide.

Dissemination


Papers:

 

Communications:

  1. I. Podolean, O. D. Pavel, H.G. Manyar, K. Ralphs, P. Goodrich, S.F.R. Taylor, V.I. Parvulescu, C. Hardacre; The 8th Tokyo Conference on Advanced Catalytic Science and Technology (TOCAT8), YOKOHAMA, Japan, August 5 – 10, 2018 (Poster)

  2. I. Podolean, V. I. Parvulescu, M. Andruh; 14th Pannonian International Symposium on Catalysis; Starý Smokovec, Slovak Republic, September 3-7, 2018 (Poster)


Phase II/2019 
(01.01.2019-31.12.2019): Immobilization of [CuIILnIII] complex on the graphene. 

Activity 2.1.  Covalent immobilization of complex on the graphene;

Activity 2.2.  Step by step construction of the complex with compartmental ligand on the graphene surface;

Activity 2.3.  Immobilization of complex by anion exchange;

 

Phase III/2020 (01.01.2020-30.04.2020)Optimization of the catalytic system.

 

Activity 3.1. Optimization of heterogeneous catalytic system for oxidative cross coupling reaction;