title: p-Tolylimido rhenium(V) complexes - synthesis, X-ray studies, spectroscopic characterization, DFT calculations and catalytic activity.
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]·1/2H2O (6) were synthesized. The compounds were identified by elemental analysis, IR, NMR ((1)H, (13)C and (31)P), 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, and 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 the PBE1PBE functional. Additional information about bonding in the compounds [Re(p-NC6H4CH3)Cl2(py-2-COO)(PPh3)] was obtained by NBO analysis. The catalytic activity of the complexes incorporating the picolinate ligand was studied and compared in the synthesis of N-substituted ethyl glycine esters from ethyl diazoacetate and amines.
authors: Department of Crystallography, Institute of Chemistry, University of Silesia, 9th Szkolna St., 40-006 Katowice, Poland. basia@ich.us.edu.pl.
authors: Barbara
authors: B
authors: Machura
authors: Izabela
authors: I
authors: Gryca
authors: Jan Grzegorz
authors: JG
authors: Małecki
authors: Francisco
authors: F
authors: Alonso
authors: Yanina
authors: Y
authors: Moglie
mesh_terms: D002384:Catalysis; D060326:Chemistry Techniques, Synthetic; D018360:Crystallography, X-Ray; D004583:Electrons; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D011789:Quantum Theory; D012211:Rhenium / Q000737:chemistry*; D013057:Spectrum Analysis
chemical_list: D009942:Organometallic Compounds; D012211:Rhenium