Isovalent and mixed-valent molybdenum complexes containing MoV(μ-E)(μ-S2)MoV/IV (E=O, S) core units

2.50
Hdl Handle:
http://hdl.handle.net/2173/108830
Title:
Isovalent and mixed-valent molybdenum complexes containing MoV(μ-E)(μ-S2)MoV/IV (E=O, S) core units
Authors:
Gourlay, Craig; Taylor, Michelle K.; Smith, Paul D.; Young, Charles G.
Citation:
Inorganica Chimica Acta, 2010, vol. 363, no. 6, pp. 1126 -1132
Publisher:
Elsevier
Issue Date:
2010
URI:
http://hdl.handle.net/2173/108830
DOI:
10.1016/j.ica.2009.09.033
Additional Links:
http://www.elsevier.com/locate/ica
Abstract:
The reactions of TpiPrMoO(SR)(NCMe) (TpiPr = hydrotris(3-isopropylpyrazolyl)borate) with propylene sulfide in toluene result in the formation of the diamagnetic, isovalent Mo(V) complex, [TpiPrMoVO]2(μ-S)(μ-S2). This complex and its previously reported μ-oxo analog, [TpiPrMoVO]2(μ-O)(μ-S2), react with cobaltocene to produce one-electron-reduced, mixed-valent complexes, [CoCp2][{TpiPrMoIV,VO}2(μ-E)(μ-S2)] (E = S or O, respectively). All complexes have been isolated and characterized by microanalysis, mass spectrometry, IR and 1H NMR or EPR spectroscopies, and X-ray crystallography. Neutral [TpiPrMoVO]2(μ-S)(μ-S2) exhibits a pseudo-C2 symmetric structure, with distorted octahedral anti oxo-Mo(IV) centers coordinated by TpiPr and linked by μ-sulfido and μ-disulfido ligands. A similar structure is adopted by the anion in mixed-valent [CoCp2][{TpiPrMoIV,VO}2(μ-S)(μ-S2)]; this compound adopts a hexagonal, supramolecular structure with columns of tight ion-pairs with View the MathML source interactions, interconnected through weaker View the MathML source contacts to three neighboring columns. The structure contains large interstitial voids filled with lattice solvent molecules. EPR investigation of the mixed-valent complexes gave rise to unusually broad signals with no evident hyperfine splitting. The synthesis and characterization of a number of cis-dioxo-Mo(VI) precursors are also reported.
Type:
Article
Language:
en
Description:
Full-text of this article is not available in this e-prints service. This article was originally published following peer-review in Inorganica Chimica Acta, published by and copyright Elsevier.
ISSN:
0020-1693
EISSN:
1873-3255

Full metadata record

DC FieldValue Language
dc.contributor.authorGourlay, Craigen
dc.contributor.authorTaylor, Michelle K.en
dc.contributor.authorSmith, Paul D.en
dc.contributor.authorYoung, Charles G.en
dc.date.accessioned2010-08-02T13:47:11Z-
dc.date.available2010-08-02T13:47:11Z-
dc.date.issued2010-
dc.identifier.citationInorganica Chimica Acta, 2010, vol. 363, no. 6, pp. 1126 -1132en
dc.identifier.issn0020-1693-
dc.identifier.doi10.1016/j.ica.2009.09.033-
dc.identifier.urihttp://hdl.handle.net/2173/108830-
dc.descriptionFull-text of this article is not available in this e-prints service. This article was originally published following peer-review in Inorganica Chimica Acta, published by and copyright Elsevier.en
dc.description.abstractThe reactions of TpiPrMoO(SR)(NCMe) (TpiPr = hydrotris(3-isopropylpyrazolyl)borate) with propylene sulfide in toluene result in the formation of the diamagnetic, isovalent Mo(V) complex, [TpiPrMoVO]2(μ-S)(μ-S2). This complex and its previously reported μ-oxo analog, [TpiPrMoVO]2(μ-O)(μ-S2), react with cobaltocene to produce one-electron-reduced, mixed-valent complexes, [CoCp2][{TpiPrMoIV,VO}2(μ-E)(μ-S2)] (E = S or O, respectively). All complexes have been isolated and characterized by microanalysis, mass spectrometry, IR and 1H NMR or EPR spectroscopies, and X-ray crystallography. Neutral [TpiPrMoVO]2(μ-S)(μ-S2) exhibits a pseudo-C2 symmetric structure, with distorted octahedral anti oxo-Mo(IV) centers coordinated by TpiPr and linked by μ-sulfido and μ-disulfido ligands. A similar structure is adopted by the anion in mixed-valent [CoCp2][{TpiPrMoIV,VO}2(μ-S)(μ-S2)]; this compound adopts a hexagonal, supramolecular structure with columns of tight ion-pairs with View the MathML source interactions, interconnected through weaker View the MathML source contacts to three neighboring columns. The structure contains large interstitial voids filled with lattice solvent molecules. EPR investigation of the mixed-valent complexes gave rise to unusually broad signals with no evident hyperfine splitting. The synthesis and characterization of a number of cis-dioxo-Mo(VI) precursors are also reported.en
dc.language.isoenen
dc.publisherElsevieren
dc.relation.urlhttp://www.elsevier.com/locate/icaen
dc.titleIsovalent and mixed-valent molybdenum complexes containing MoV(μ-E)(μ-S2)MoV/IV (E=O, S) core unitsen
dc.typeArticleen
dc.identifier.eissn1873-3255-
All Items in e-space are protected by copyright, with all rights reserved, unless otherwise indicated.