Please use this identifier to cite or link to this item: http://hdl.handle.net/2440/100792
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Type: Journal article
Title: d¹ oxosulfido-Mo(V) compounds: first isolation and unambiguous characterization of an extended series
Other Titles: d(1) oxosulfido-Mo(V) compounds: first isolation and unambiguous characterization of an extended series
Author: Doonan, C.
Gourlay, C.
Nielsen, D.
Ng, V.
Smith, P.
Evans, D.
George, G.
White, J.
Young, C.
Citation: Inorganic Chemistry, 2015; 54(13):6386-6396
Publisher: American Chemical Society
Issue Date: 2015
ISSN: 0020-1669
1520-510X
Statement of
Responsibility: 
Christian J. Doonan, Craig Gourlay, David J. Nielsen, Victor W. L. Ng, Paul D. Smith, David J. Evans, Graham N. George, Jonathan M. White, and Charles G. Young
Abstract: Reaction of Tp(iPr)Mo(VI)OS(OAr) with cobaltocene in toluene results in the precipitation of brown, microcrystalline oxosulfido-Mo(V) compounds, [CoCp2][Tp(iPr)Mo(V)OS(OAr)] (Cp(-) = η(5)-C5H5(-), Tp(iPr)(-) = hydrotris(3-isopropylpyrazol-1-yl)borate, OAr(-) = phenolate or 2-(s)Bu, 2-(t)Bu, 3-(t)Bu, 4-(s)Bu, 4-Ph, 3,5-(s)Bu2, 2-CO2Me, 2-CO2Et or 2-CO2Ph derivative thereof). The compounds are air- and water-sensitive and display ν(Mo═O) and ν(Mo[Formula: see text]S) IR absorption bands at ca. 890 and 435 cm(-1), respectively, 20-40 cm(-1) lower in energy than the corresponding bands in Tp(iPr)MoOS(OAr). They are electrochemically active and exhibit three reversible cyclovoltammetric waves (E(Mo(VI)/Mo(V)) = -0.40 to -0.66 V, E([CoCp2](+)/CoCp2) = -0.94 V and E(CoCp2/[CoCp2](-)) = -1.88 V vs SCE). Structural characterization of [CoCp2][Tp(iPr)MoOS(OC6H4CO2Et-2)]·2CH2Cl2 revealed a distorted octahedral Mo(V) anion with Mo═O and Mo[Formula: see text]S distances of 1.761(5) and 2.215(2) Å, respectively, longer than corresponding distances in related Tp(iPr)MoOS(OAr) compounds. The observation of strong S(1s) → (S(3p) + Mo(4d)) S K-preedge transitions indicative of a d(1) sulfido-Mo(V) moiety and the presence of short Mo═O (ca. 1.72 Å) and Mo[Formula: see text]S (ca. 2.25 Å) backscattering contributions in the Mo K-edge EXAFS further support the oxosulfido-Mo(V) formulation. The compounds are EPR-active, exhibiting highly anisotropic (Δg 0.124-0.150), rhombic, frozen-glass spectra with g1 close to the value observed for the free electron (ge = 2.0023). Spectroscopic studies are consistent with the presence of a highly covalent Mo[Formula: see text]S π* singly occupied molecular orbital. The compounds are highly reactive, with reactions localized at the terminal sulfido ligand. For example, the compounds react with cyanide and PPh3 to produce thiocyanate and SPPh3, respectively, and various (depending on solvent) oxo-Mo(V) species. Reactions with copper reagents also generally lead to desulfurization and the formation of oxo-Mo(V) or -Mo(IV) complexes.
Keywords: Sulfides
Description: Published: June 5, 2015
Rights: © 2015 American Chemical Society
RMID: 0030036708
DOI: 10.1021/acs.inorgchem.5b00708
Appears in Collections:Chemistry publications

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