2024-03-28T17:03:54Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1903042023-01-23T08:13:47Zcom_10261_135com_10261_4col_10261_388
00925njm 22002777a 4500
dc
Reviejo, I.
author
Tabernero, V.
author
Mosquera, Marta E.G.
author
Ramos, Javier
author
Cuenca, Tomás
author
Jiménez, G.
author
2018-07-09
The reaction of TiCl(OPr) (n = 0, 2, 4) with various terpenoid preligands based on α-pinene, CHMe(OH)(NCHCHG) (G = NH, I; NHMe, II; OH, III), stereoselectively affords a series of new chiral titanium(IV) complexes. Such complexes are either octahedral, [TiClX(OCHMeNCHCHG-κN,N,O)] (X = Cl, G = NH, 1; X = OPr, G = NH, 2; G = NHMe, 3), or trigonal bipyramidal, [Ti(OPr)(OCHMeNCHCHG-κN,O)] (G = NH, 4; NHMe, 5) and [TiX(OPr)(OCHMeNCHCHO-κN,O,O∗)] (X = Cl, 6; OPr, 8), depending on the acidity of titanium, the reaction conditions and the nature of the pendant ending group of the terpenoid ligand. Density functional theory (DFT) calculations have been carried out to assess the stability of the multiple possible diastereoisomers allowing us to propose structural suggestions. The new titanium complexes efficiently catalyze the selective oxidation of various types of sulfides to either sulfoxides or sulfones using aqueous hydrogen peroxide, under mild conditions. All compounds have been characterized by multinuclear NMR spectroscopy and the molecular structure for some of them has been determined by X-ray diffraction.
Organometallics 37: 3437-3449 (2018)
http://hdl.handle.net/10261/190304
10.1021/acs.organomet.8b00163
http://dx.doi.org/10.13039/501100003329
http://dx.doi.org/10.13039/501100006302
Chiral Titanium(IV) Complexes Containing Polydentate Ligands Based on α-Pinene. Catalytic Activity in Sulfoxidation with Hydrogen Peroxide