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Developing Pathways to the Synthesis of Low‐Valence Molybdenum Methoxides: Preparation, Characterization, and Redox Chemistry of Dimeric and Tetrameric Molybdenum Alkoxide Clusters
Author(s) -
Kuznetsov Denis A.,
Fedyanin Ivan V.,
Komarova Natal'ya S.,
Shilov Gennady V.,
Martynenko Vyacheslav M.,
Vasil'ev Sergey G.,
Krivenko Alexander G.,
Lyssenko Konstantin A.,
Bazhenova Tamara A.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201403032
Subject(s) - chemistry , molybdenum , alkoxide , disproportionation , redox , homoleptic , valence (chemistry) , cyclic voltammetry , inorganic chemistry , dissolution , methanol , crystallography , medicinal chemistry , catalysis , metal , electrochemistry , organic chemistry , electrode
The rare Mo=Mo double‐bonded dimeric alkoxide complex [Mo 2 Cl 4 (OCH 3 ) 4 (CH 3 OH) 2 ] ( 1 ) was prepared by the simple methanolysis reaction of [MoCl 4 (CH 3 CN) 2 ]. It was shown that the dissolution of 1 in thf results in the formation of the [Mo 2 O 2 Cl 4 (OCH 3 ) 2 (thf) 2 ] ( 2 ) and [Mo 2 Cl 4 (OCH 3 ) 4 (thf) 2 ] ( 3 ) dimers. A novel tetranuclear 10e molybdenum cluster [Mo 4 Cl 4 O 2 (OCH 3 ) 6 (CH 3 OH) 4 ] ( 4 ) was synthesized by the spontaneous disproportionation of 1 in methanol. An alternative pathway to 4 based on the redox reaction of Mo 3+ and Mo 5+ compounds {in the form of [MoCl 3 (thf) 3 ] and [Mo 2 Cl 4 (OCH 3 ) 6 ] ( 5 ), respectively} was proposed and realized. The redox behavior of 4 was investigated by means of cyclic voltammetry. It was demonstrated that 4 may undergo a reversible two‐electron reduction process, which implies the retention of the {Mo 4 } core, whereas the oxidation is irreversible, proceeding apparently with the destruction of the tetranuclear cluster core.