New Insights into the Electrochemistry of Molybdenum(VI) Dioxo Complexes Containing a Tetradentate S2(NH)2-Type Ligand

Ulrich Küsthardt, Rolf W. Albach, Paul Kiprof

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The electrochemistry of dioxomolybdenum(VI) with the tetradentate S2(NH)2-type ligand N,N′-bis(2-mercaptophenyl)-2,3-diaminobutane (mPhabH4), at neutral, acidic, and basic conditions, has been investigated. The molecular structure of (mPhabH2)MoVIO2 (1) has been determined: space group P212121 (No. 19), a = 8.667(<1), b = 12.884(<1), c = 19.877(3) Å, V= 2220 Å3; Z = 4. The cis-dioxo complex 1 displays a highly distorted octahedral structure. Electrochemical, one-electron reduction of the Mo(VI) compound 1 is followed by a fast dehydration reaction leading to [(mPhab)MoO] (4), which can be further reduced in a subsequent one-electron reduction step to the Mo(IV) dianion. At neutral conditions this process appears as a single two-electron reduction. Upon addition of N-methylimidazole (NMI) the dehydration rate decreases and two separate reduction steps can be observed. Acidic conditions also lead to a decrease of the dehydration rate and to two separate one-electron reductions. In basic solution the Mo(VI) complex 1 is reduced by methanol to [(mPhab)MovO] (4), which shows both a quasi-reversible one-electron reduction wave to form the Mo(IV) dianion and a quasi-reversible oxidation wave. Synthetically, [(mPhab)MovO] (4) can also be obtained via deoxygenation of 1 by Ph2PMe in the presence of N-methylimidazole, presumably via formation of a Mo(IV)-NMI adduct that undergoes a comproportionation reaction with 1 and subsequent dehydration to the mononuclear Mo(V) complex 4. Neither μ-oxo-bridged Mo(V) dimers nor mononuclear Mo(IV) species can be detected.

Original languageEnglish (US)
Pages (from-to)1838-1843
Number of pages6
JournalInorganic Chemistry
Issue number9
StatePublished - Jan 1 1993

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