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

doi:10.3390/molecules19067094

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

Molecules. 2014 May 30;19(6):7094-103. doi: 10.3390/molecules19067094.

Authors

Alexander Y Kostukovich¹, Dmitrii I D'yachihin², Fedor M Dolgushin³, Alexander F Smol'yakov⁴, Ivan A Godovikov⁵, Igor T Chizhevsky⁶

Affiliations

¹ A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia. dftblyp@gmail.com.
² A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia. dyachihin@list.ru.
³ A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia. fedya@xrlab.ineos.ac.ru.
⁴ A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia. rengenhik@gmail.com.
⁵ A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia. pr0vider@ineos.ac.ru.
⁶ A.N. Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991 Moscow, Russia. chizbor@ineos.ac.ru.

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.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Ligands*
Molecular Structure
Oxygen / chemistry*
X-Ray Diffraction

Substances

Ligands
Oxygen