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 |
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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 |
Files in This Item:
File | Description | Size | Format | |
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2013_Machura_etal_DaltonTransactions.pdf | Accepted Manuscript | 4,09 MB | Adobe PDF | Open Preview |
2013_Machura_etal_DaltonTransactions_REV.pdf | Versión revisada | 4,77 MB | Adobe PDF | Open Preview |
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