title: Synthesis, structure, and reactivity of mononuclear RE(I) oximato complexes.
abstract: Complexes [Re(ONCMe2)(CO)3(bipy)] (1) and [Re(ONCMe2)(CO)3(phen)] (2), synthesized by reaction of the respective triflato precursors [Re(OTf)(CO)3(N-N)] (N-N = bipy, phen) with KONCMe2, feature O-bonded monodentate oximato ligands. Compound [Re(CO)3(phen)(HONCMe2)]BAr'4 (3), with a monodentate N-bonded oxime ligand, was prepared by reaction of [Re(OTf)(CO)3(phen)], HONCMe2, and NaBAr'4. Deprotonation of 3 afforded 2. The oximato complexes reacted with p-tolylisocyanate, p-tolylisothiocyanate, maleic anhydride, and tetracyanoethylene, affording the products of the insertion of the electrophile into the Re-O bond, compounds 4-7. One representative of each type of compound was fully characterized, including single-crystal X-ray diffraction. The reactions of 1 and 2 with dimethylacetylenedicarboxylate were found to involve first an insertion as the ones mentioned above but followed by incorporation of water, loss of acetone, and formation of the charge-separated neutral amido complexes 9 and 10. The structure of 9 and 10 was determined by X-ray diffraction, and key features of their electronic distribution were studied using a topological analysis of the electron density as obtained from the Fourier map.
authors.affiliation: Departamento de Química OrgAnica e InorgAnica -IUQOEM, Facultad de Química, Universidad de Oviedo-CSIC, 33006 Oviedo, Spain.
authors.forename: Luciano
authors.initials: L
authors.lastname: Cuesta
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Huertos
authors.forename: Dolores
authors.initials: D
authors.lastname: Morales
authors.forename: Julio
authors.initials: J
authors.lastname: Pérez
authors.forename: Lucía
authors.initials: L
authors.lastname: Riera
authors.forename: Víctor
authors.initials: V
authors.lastname: Riera
authors.forename: Daniel
authors.initials: D
authors.lastname: Miguel
authors.forename: Amador
authors.initials: A
authors.lastname: Menéndez-Velazquez
authors.forename: Santiago
authors.initials: S
authors.lastname: García-Granda