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
Alexander Y. Kostukovich,
Dmitrii I. D'yachihin,
Fedor M. Dolgushin,
Alexander F. Smol'yakov,
Ivan A. Godovikov,
Igor T. Chizhevsky
Affiliations
Alexander Y. Kostukovich
A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia
Dmitrii I. D'yachihin
A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia
Fedor M. Dolgushin
A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia
Alexander F. Smol'yakov
A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia
Ivan A. Godovikov
A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia
Igor T. Chizhevsky
A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia
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.
