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Title: New insights into the electrochemistry of molybdenum(VI) dioxo complexes containing a tetradentate S[sub 2](NH)[sub 2]-type ligand

Abstract

The electrochemistry of dioxomolybdenum(VI) with the tetradentate S[sub 2](NH)[sub 2]-type ligand N,N[prime]-bis(2-mercaptophenyl)-2,3-diaminobutane (mPhabH[sub 4]), at neutral, acidic, and basic conditions, has been investigated. The molecular structure of (mPhabH[sub 2])Mo[sup VI]O[sub 2] (1) has been determined: space group P2[sub 1]2[sub 1]2[sub 1] (No. 19), a = 8.667(<1), b = 12.884(<1), c = 19.877(3) [Angstrom], V = 2220 [Angstrom][sup 3]; 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][sup [minus]] (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)Mo[sub V]O][sup [minus]] (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)Mo[sup V]O][sup [minus]] (4) can also be obtained via deoxygenation of 1 by Ph[submore » 2]PMe 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 [mu]-oxo-bridged Mo(V) dimers nor mononuclear Mo(IV) species can be detected. 30 refs., 5 figs., 4 tabs.« less

Authors:
; ;  [1]
  1. Technischen Universitaet Muenchen, Garching (Germany)
Publication Date:
OSTI Identifier:
6046788
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (United States)
Additional Journal Information:
Journal Volume: 32:9; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MOLYBDENUM COMPLEXES; ELECTROCHEMISTRY; MOLYBDENUM OXIDES; AMINES; AROMATICS; CRYSTAL STRUCTURE; DEHYDRATION; DIMERS; LATTICE PARAMETERS; LIGANDS; METHANOL; MOLECULAR STRUCTURE; NITRIC OXIDE; OXIDATION; PH VALUE; REDUCTION; THIOLS; X-RAY DIFFRACTION; ALCOHOLS; CHALCOGENIDES; CHEMICAL REACTIONS; CHEMISTRY; COHERENT SCATTERING; COMPLEXES; DIFFRACTION; HYDROXY COMPOUNDS; MOLYBDENUM COMPOUNDS; NITROGEN COMPOUNDS; NITROGEN OXIDES; ORGANIC COMPOUNDS; ORGANIC SULFUR COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; REFRACTORY METAL COMPOUNDS; SCATTERING; TRANSITION ELEMENT COMPLEXES; TRANSITION ELEMENT COMPOUNDS; 400201* - Chemical & Physicochemical Properties

Citation Formats

Kuesthardt, U, Albach, R W, and Kiprof, P. New insights into the electrochemistry of molybdenum(VI) dioxo complexes containing a tetradentate S[sub 2](NH)[sub 2]-type ligand. United States: N. p., 1993. Web. doi:10.1021/ic00061a048.
Kuesthardt, U, Albach, R W, & Kiprof, P. New insights into the electrochemistry of molybdenum(VI) dioxo complexes containing a tetradentate S[sub 2](NH)[sub 2]-type ligand. United States. doi:10.1021/ic00061a048.
Kuesthardt, U, Albach, R W, and Kiprof, P. Wed . "New insights into the electrochemistry of molybdenum(VI) dioxo complexes containing a tetradentate S[sub 2](NH)[sub 2]-type ligand". United States. doi:10.1021/ic00061a048.
@article{osti_6046788,
title = {New insights into the electrochemistry of molybdenum(VI) dioxo complexes containing a tetradentate S[sub 2](NH)[sub 2]-type ligand},
author = {Kuesthardt, U and Albach, R W and Kiprof, P},
abstractNote = {The electrochemistry of dioxomolybdenum(VI) with the tetradentate S[sub 2](NH)[sub 2]-type ligand N,N[prime]-bis(2-mercaptophenyl)-2,3-diaminobutane (mPhabH[sub 4]), at neutral, acidic, and basic conditions, has been investigated. The molecular structure of (mPhabH[sub 2])Mo[sup VI]O[sub 2] (1) has been determined: space group P2[sub 1]2[sub 1]2[sub 1] (No. 19), a = 8.667(<1), b = 12.884(<1), c = 19.877(3) [Angstrom], V = 2220 [Angstrom][sup 3]; 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][sup [minus]] (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)Mo[sub V]O][sup [minus]] (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)Mo[sup V]O][sup [minus]] (4) can also be obtained via deoxygenation of 1 by Ph[sub 2]PMe 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 [mu]-oxo-bridged Mo(V) dimers nor mononuclear Mo(IV) species can be detected. 30 refs., 5 figs., 4 tabs.},
doi = {10.1021/ic00061a048},
journal = {Inorganic Chemistry; (United States)},
issn = {0020-1669},
number = ,
volume = 32:9,
place = {United States},
year = {1993},
month = {4}
}