Please use this identifier to cite or link to this item: https://hdl.handle.net/1959.11/7540
Title: Isovalent and mixed-valent molybdenum complexes containing MoV(μ-E)(μ-S2)MoV/IV (E = O, S) core units
Contributor(s): Gourlay, C (author); Taylor, Michelle Keily  (author); Smith, PD (author); Young, CG (author)
Publication Date: 2010
DOI: 10.1016/j.ica.2009.09.033
Handle Link: https://hdl.handle.net/1959.11/7540
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 (μ-S2)...CoCp2+ interactions, interconnected through weaker (μ-S2)...CoCp2+ 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.
Publication Type: Journal Article
Source of Publication: Inorganica Chimica Acta, 363(6), p. 1126-1132
Publisher: Elsevier BV
Place of Publication: Netherlands
ISSN: 1873-3255
0020-1693
Fields of Research (FoR) 2008: 030207 Transition Metal Chemistry
030201 Bioinorganic Chemistry
Socio-Economic Objective (SEO) 2008: 970103 Expanding Knowledge in the Chemical Sciences
Peer Reviewed: Yes
HERDC Category Description: C1 Refereed Article in a Scholarly Journal
Appears in Collections:Journal Article

Files in This Item:
3 files
File Description SizeFormat 
Show full item record

SCOPUSTM   
Citations

10
checked on Jul 6, 2024

Page view(s)

1,188
checked on Mar 31, 2024
Google Media

Google ScholarTM

Check

Altmetric


Items in Research UNE are protected by copyright, with all rights reserved, unless otherwise indicated.