title: Oxorhenium(V) complexes with phenolate-oxazoline ligands: influence of the isomeric form on the O-atom-transfer reactivity.
abstract: The bidentate phenolate-oxazoline ligands 2-(2'-hydroxyphenyl)-2-oxazoline (1a, Hoz) and 2-(4',4'-dimethyl-3',4'-dihydrooxazol-2'-yl)phenol (1b, Hdmoz) were used to synthesize two sets of oxorhenium(V) complexes, namely, [ReOCl2(L)(PPh3)] [L = oz (2a) and dmoz (2b)] and [ReOX(L)2] [X = Cl, L = oz (3a or 3a'); X = Cl, L = dmoz (3b); X = OMe, L = dmoz (4)]. Complex 3a' is a coordination isomer (N,N-cis isomer) with respect to the orientation of the phenolate-oxazoline ligands of the previously published complex 3a (N,N-trans isomer). The reaction of 3a' with silver triflate in acetonitrile led to the cationic compound [ReO(oz)2(NCCH3)](OTf) ([3a'](OTf)). Compound 4 is a rarely observed isomer with a trans-O═Re-OMe unit. Complexes 3a, 3a', [3a'](OTf), and 4 were tested as catalysts in the reduction of a perchlorate salt with an organic sulfide as the O acceptor and found to be active, in contrast to 2a and 2b. A comparison of the two isomeric complexes 3a and 3a' showed significant differences in activity: 87% 3a vs 16% 3a' sulfoxide yield. When complex [3a'](OTf) was used, the yield was 57%. Density functional theory calculations circumstantiate all of the proposed intermediates with N,N-trans configurations to be lower in energy compared to the respective compounds with N,N-cis configurations. Also, no interconversions between N,N-trans and N,N-cis configurations are predicted, which is in accordance with experimental data. This is interesting because it contradicts previous mechanistic views. Kinetic analyses determined by UV-vis spectroscopy on the rate-determining oxidation steps of 3a, 3a', and [3a'](OTf) proved the N,N-cis complexes 3a' and [3a'](OTf) to be slower by a factor of ∼4.
authors.affiliation: Institute of Chemistry, University of Graz , Schubertstrasse 1, 8010 Graz, Austria.
authors.forename: Jörg A
authors.initials: JA
authors.lastname: Schachner
authors.forename: Belina
authors.initials: B
authors.lastname: Terfassa
authors.forename: Lydia M
authors.initials: LM
authors.lastname: Peschel
authors.forename: Niklas
authors.initials: N
authors.lastname: Zwettler
authors.forename: Ferdinand
authors.initials: F
authors.lastname: Belaj
authors.forename: Pawel
authors.initials: P
authors.lastname: Cias
authors.forename: Georg
authors.initials: G
authors.lastname: Gescheidt
authors.forename: Nadia C
authors.initials: NC
authors.lastname: Mösch-Zanetti
mesh_terms: D002384:Catalysis; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007536:Isomerism; D008024:Ligands; D008958:Models, Molecular; D010080:Oxazoles / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010472:Perchlorates / Q000737:chemistry; D010636:Phenols / Q000138:chemical synthesis / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D008024:Ligands; D010080:Oxazoles; D010472:Perchlorates; D010636:Phenols; C015428:perrhenate; D012211:Rhenium; C494474:perchlorate