title: Octahedral manganese(i) and ruthenium(ii) complexes containing 2-(methylamido)pyridine-borane as a tripod κ3N,H,H-ligand.
abstract: The borane adduct of the 2-(methylamido)pyridine anion, [mapyBH3]-, has been incorporated into octahedral metal complexes. In fac-[Mn(κ3N,H,H-mapyBH3)(CO)3] (1) and fac-[RuH(κ3N,H,H-mapyBH3)(CO)(PiPr3)] (2), which have been prepared by treating K[mapyBH3] with fac-[MnBr(MeCN)2(CO)3] and [RuHCl(CO)(PiPr3)2], respectively, it behaves as a tripod ligand, attached to the metal atom through the amido N atom and through two H atoms of the BH3moiety. X-ray diffraction analyses and theoretical studies (DFT, QTAIM) have shown that the MH2B atom grouping of 1 and 2 comprises two 3c-2e M-H-B interactions that are between those of the Shimoi type (κ1H coordination of the B-H bond) and those of the agostic type (κ2B,H coordination of the B-H bond). However, while both M-H-B interactions are almost identical in complex 1, this is not the case in complex 2, in which one M-H-B interaction is more agostic than the other due to the different trans influence of the hydride and phosphane ligands.
authors.affiliation: Centro de Innovación en Química Avanzada (ORFEO-CINQA), Departamento de Química Orgánica e Inorgánica-IUQOEM, Universidad de Oviedo-CSIC, 33071 Oviedo, Spain. jac@uniovi.es.
authors.forename: Javier
authors.initials: J
authors.lastname: Brugos
authors.affiliation: Centro de Innovación en Química Avanzada (ORFEO-CINQA), Departamento de Química Orgánica e Inorgánica-IUQOEM, Universidad de Oviedo-CSIC, 33071 Oviedo, Spain. jac@uniovi.es.
authors.forename: Javier A
authors.identifier: http://orcid.org/0000-0001-8563-9193
authors.initials: JA
authors.lastname: Cabeza
authors.affiliation: Centro de Innovación en Química Avanzada (ORFEO-CINQA), Departamento de Química Orgánica e Inorgánica-IUQOEM, Universidad de Oviedo-CSIC, 33071 Oviedo, Spain. jac@uniovi.es.
authors.forename: Pablo
authors.initials: P
authors.lastname: García-Álvarez
authors.affiliation: Departamento de Química Física y Analítica, Universidad de Oviedo, 33071 Oviedo, Spain.
authors.forename: Enrique
authors.initials: E
authors.lastname: Pérez-Carreño
authors.affiliation: Departamento de Química Física y Analítica, Universidad de Oviedo, 33071 Oviedo, Spain.
authors.forename: Juan F
authors.initials: JF
authors.lastname: Van der Maelen