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Immobilization of copper complexes with (1,10-phenanthrolinyl)phosphonates on titania supports for sustainable catalysis


Different strategies for the immobilization of copper complexes with 1,10-phenanthroline (phen) using the phosphonate anchoring group were investigated to prepare robust and porous heterogeneous catalysts. Homoleptic and heteroleptic copper(I) complexes with phen bearing the bis(trimethylsiloxy)phosphoryl anchoring group (Pphen-Si) at different positions of phen backbone were prepared and covalently incorporated into titania (TiO2) xerogels by using the sol-gel process or grafted onto a surface of mesoporous TiO2 (SBET = 650 m2 g-1). Copper(I) bis(Pphen-Si) complexes were the only complexes that were successfully anchored onto TiO2 surface because the heterogenization was often accompanied by undesirable dissociation of copper complexes. Hybrid materials based on copper(I) chelates with one phen ligand were obtained following a two-step procedure involving the immobilization of Pphen-Si chelators and their successive complexation with copper(I) ions. Most porous material Cu/6b/SM/A displaying BET surface area of 243 m2 g-1 and bearing 0.57 mmol g-1 of the complex was synthesized according to the surface modification of TiO2. Excellent catalytic performance of the reusable Cu/6b/SM/A material in the Sonogashira-type coupling and the Huisgen 1,3-dipolar cycloaddition was also demonstrated. This solid represents the first example of mesoporous TiO2-supported transition metal catalysts

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Publication details

The article was received on 08 Feb 2017, accepted on 11 May 2017 and first published on 12 May 2017

Article type: Paper
DOI: 10.1039/C7TA01195D
Citation: J. Mater. Chem. A, 2017, Accepted Manuscript
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    Immobilization of copper complexes with (1,10-phenanthrolinyl)phosphonates on titania supports for sustainable catalysis

    A. Yu. Mitrofanov, S. Brandès, F. herbst, S. Rigolet, A. Lemeune and I. P. Beletskaya, J. Mater. Chem. A, 2017, Accepted Manuscript , DOI: 10.1039/C7TA01195D

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