title: An unusual conversion of paramagnetic [3-Cl-3,3,8-{Ph2P(CH2)nPPh-µ-(C6H4-ortho)}-1,2-(CH3)2-closo-3,1,2-RuIIIC2B9H8] (n=3 and 4) to form the first 18-electron P-phenylene ortho-cycloboronated closo-ruthenacarboranes with a dioxygen ligand.
abstract: Treatment of [3-Cl-3,3,8-[Ph2P(CH2)nPPh-µ-(C6H4-ortho)]-1,2-Me2-closo-3,1,2-RuIIIC2B9H8] (1, n=3; 2, n=4) with an excess of KOH in a 1:1 benzene/methanol mixture at room temperature in air affords new dioxygen closo-ruthenacarborane complexes [3-(η2-O2)-3,3,8-[Ph2P(CH2)nPPh-µ-(C6H4-ortho)]-1,2-Me2-closo-3,1,2-RuIIIC2B9H8] (3, n=3) and (4, n=4) in 42.5% and 45.8% yield respectively. The structures of dioxygen complexes 3 and 4 were established by single-crystal X-ray diffraction. The IR and multinuclear NMR data [1H, 13C{1H}, 31P{1H} and 11B{1H}] along with 2D HSQC correlation spectra for the new dioxygen closo-ruthenacarboranes are discussed.
authors.affiliation: A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia. dftblyp@gmail.com.
authors.forename: Alexander Y
authors.initials: AY
authors.lastname: Kostukovich
authors.affiliation: A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia. dyachihin@list.ru.
authors.forename: Dmitrii I
authors.initials: DI
authors.lastname: D'yachihin
authors.affiliation: A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia. fedya@xrlab.ineos.ac.ru.
authors.forename: Fedor M
authors.initials: FM
authors.lastname: Dolgushin
authors.affiliation: A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia. rengenhik@gmail.com.
authors.forename: Alexander F
authors.initials: AF
authors.lastname: Smol'yakov
authors.affiliation: A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia. pr0vider@ineos.ac.ru.
authors.forename: Ivan A
authors.initials: IA
authors.lastname: Godovikov
authors.affiliation: A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia. chizbor@ineos.ac.ru.
authors.forename: Igor T
authors.initials: IT
authors.lastname: Chizhevsky
mesh_terms: D008024:Ligands; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D008024:Ligands; D010100:Oxygen