p-Tolylimido rhenium(V) complexes – Synthesis, X-ray studies, spectroscopic characterization, DFT calculations and catalytic activity

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Title: p-Tolylimido rhenium(V) complexes – Synthesis, X-ray studies, spectroscopic characterization, DFT calculations and catalytic activity
Authors: Machura, Barbara | Gryca, Izabela | Grzegorz Małecki, Jan | Alonso, Francisco | Moglie, Yanina
Research Group/s: Nuevos Materiales y Catalizadores (MATCAT)
Center, Department or Service: Universidad de Alicante. Departamento de Química Orgánica
Keywords: Rhenium complexes | Bidentate ligands | Catalysts | X-ray structures | Glycine derivatives
Knowledge Area: Química Orgánica
Issue Date: 21-Nov-2013
Publisher: Royal Society of Chemistry
Citation: Dalton Transactions. 2013, Accepted Manuscript. doi:10.1039/C3DT52528G
Abstract: Novel p-tolylimido rhenium(V) complexes trans-(Cl,Cl)-[Re(p-NC6H4CH3)Cl2(py-2-COO)(PPh3)]·MeCN (1a), trans-(Cl,Cl)-[Re(p-NC6H4CH3)Cl2(py-2-COO)(PPh3)] (1b), trans-(Br,Br)-[Re(p-NC6H4CH3)Br2(py-2-COO)(PPh3)] (2), cis-(Cl,Cl)-[Re(p-NC6H4CH3)Cl2(py-2-COO)(PPh3)] (3), cis-(Br,Br)-[Re(p-NC6H4CH3)Br2(py-2-COO)(PPh3)]·H2O (4), trans-(Cl,Cl)-[Re(p-NC6H4CH3)Cl2(OMe)] (5) and trans-(Br,Br)-[Re(p-NC6H4CH3)Br2(OMe)(PPh3)2]·½H2O (6) were synthesized. The compounds were identified by elemental analysis IR, NMR (1H, 13C and 31P), UV-Vis spectroscopy and X-ray crystallography. Calculations at the DFT level were undertaken in order to elucidate the structural, spectroscopic and bonding properties of the trans-(Cl,Cl) and cis-(Cl,Cl) isomers of [Re(p-NC6H4CH3)Cl2(py-2-COO)(PPh3)]. In the first step, extended tests of the ability of different DFT methods (B3LYP, BP86, PBE1PBE) were performed to find the best overall performer in describing the geometry of the imido Re(V) complexes; then, the electronic spectra of the trans and cis isomers of [Re(p-NC6H4CH3)Cl2(py-2-COO)(PPh3)] were investigated at the TDDFT level employing PBE1PBE functional. Additional information about bonding in the compounds [Re(p-NC6H4CH3)Cl2(py-2-COO)(PPh3)] were obtained by NBO analysis. The catalytic activity of the complexes incorporating picolinate ligand was studied and compared in the synthesis of N-substituted ethyl glycine esters from ethyl diazoacetate and amines.
Sponsor: This work was generously supported by the Spanish Ministerio de Economía y Competitividad (MINECO; CTQ2007-65218 and Consolider Ingenio 2010-CSD2007-00006), the Generalitat Valenciana (GV; PROMETEO/2009/039), and Fondo Europeo de Desarrollo Regional (FEDER). Y. M. acknowledges the Instituto de Síntesis Orgánica (ISO) of the Universidad de Alicante for a grant.
URI: http://hdl.handle.net/10045/34170
ISSN: 1477-9226 (Print) | 1477-9234 (Online)
DOI: 10.1039/C3DT52528G
Language: eng
Type: info:eu-repo/semantics/article
Rights: © Royal Society of Chemistry 2013
Peer Review: si
Publisher version: http://dx.doi.org/10.1039/C3DT52528G
Appears in Collections:INV - MATCAT - Artículos de Revistas

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