title: Ligand "Brackets" for Ga-Ga Bond.
abstract: The reactivity of digallane (dpp-Bian)Ga-Ga(dpp-Bian) (1) (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) toward acenaphthenequinone (AcQ), sulfur dioxide, and azobenzene was investigated. The reaction of 1 with AcQ in 1:1 molar ratio proceeds via two-electron reduction of AcQ to give (dpp-Bian)Ga(μ2-AcQ)Ga(dpp-Bian) (2), in which diolate [AcQ](2-) acts as "bracket" for the Ga-Ga bond. The interaction of 1 with AcQ in 1:2 molar ratio proceeds with an oxidation of the both dpp-Bian ligands as well as of the Ga-Ga bond to give (dpp-Bian)Ga(μ2-AcQ)2Ga(dpp-Bian) (3). At 330 K in toluene complex 2 decomposes to give compounds 3 and 1. The reaction of complex 2 with atmospheric oxygen results in oxidation of a Ga-Ga bond and affords (dpp-Bian)Ga(μ2-AcQ)(μ2-O)Ga(dpp-Bian) (4). The reaction of digallane 1 with SO2 produces, depending on the ratio (1:2 or 1:4), dithionites (dpp-Bian)Ga(μ2-O2S-SO2)Ga(dpp-Bian) (5) and (dpp-Bian)Ga(μ2-O2S-SO2)2Ga(dpp-Bian) (6). In compound 5 the Ga-Ga bond is preserved and supported by dithionite dianionic bracket. In compound 6 the gallium centers are bridged by two dithionite ligands. Both 5 and 6 consist of dpp-Bian radical anionic ligands. Four-electron reduction of azobenzene with 1 mol equiv of digallane 1 leads to complex (dpp-Bian)Ga(μ2-NPh)2Ga(dpp-Bian) (7). Paramagnetic compounds 2-7 were characterized by electron spin resonance spectroscopy, and their molecular structures were established by single-crystal X-ray analysis. Magnetic behavior of compounds 2, 5, and 6 was investigated by superconducting quantum interference device technique in the range of 2-295 K.
authors.affiliation: G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences , Tropinina 49, Nizhny Novgorod 603137, Russian Federation.
authors.forename: Igor L
authors.initials: IL
authors.lastname: Fedushkin
authors.affiliation: G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences , Tropinina 49, Nizhny Novgorod 603137, Russian Federation.
authors.forename: Alexandra A
authors.initials: AA
authors.lastname: Skatova
authors.affiliation: G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences , Tropinina 49, Nizhny Novgorod 603137, Russian Federation.
authors.forename: Vladimir A
authors.initials: VA
authors.lastname: Dodonov
authors.affiliation: Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University , Xi'an 710069, China.
authors.forename: Xiao-Juan
authors.initials: XJ
authors.lastname: Yang
authors.affiliation: G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences , Tropinina 49, Nizhny Novgorod 603137, Russian Federation.
authors.forename: Valentina A
authors.initials: VA
authors.lastname: Chudakova
authors.affiliation: G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences , Tropinina 49, Nizhny Novgorod 603137, Russian Federation.
authors.forename: Alexander V
authors.initials: AV
authors.lastname: Piskunov
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität , Tammannstrasse 4, Göttingen 37077, Germany.
authors.forename: Serhiy
authors.initials: S
authors.lastname: Demeshko
authors.affiliation: G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences , Tropinina 49, Nizhny Novgorod 603137, Russian Federation.
authors.forename: Evgeny V
authors.initials: EV
authors.lastname: Baranov