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https://hdl.handle.net/2440/66164
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Type: | Journal article |
Title: | Models for the Molybdenum Hydroxylases: Synthesis, Characterization and Reactivity of cis-Oxosulfido-Mo(VI) Complexes |
Author: | Doonan, C. Nielsen, D. Smith, P. White, J. George, G. Young, C. |
Citation: | Journal of the American Chemical Society, 2006; 128(1):305-316 |
Publisher: | Amer Chemical Soc |
Issue Date: | 2006 |
ISSN: | 0002-7863 1520-5126 |
Statement of Responsibility: | Christian J. Doonan, David J. Nielsen, Paul D. Smith, Jonathan M. White, Graham N. George, and Charles G. Young |
Abstract: | Atom transfer reactions have been employed to convert Tp(i)(Pr)MoO(2)(OAr) into monomeric cis-oxosulfido-Mo(VI) and dimeric mu-disulfido-Mo(V) species, [Tp(i)(Pr)MoOS(OAr)](n)() (Tp(i)(Pr) = hydrotris(3-isopropylpyrazol-1-yl)borate; OAr = phenolate or naphtholate derivative; n = 1 and 2, respectively). Dark red, monomeric Tp(i)(Pr)MoOS(OAr) complexes contain distorted octahedral cis-oxosulfido-Mo(VI) centers, with d(Mo=O) = 1.692(5) A, d(Mo=S) = 2.132(2) A, and angle(O=Mo=S) = 103.68(16) degrees for the 2-sec-butylphenolate derivative. Dark red-purple, dimeric [Tp(i)(Pr)MoOS(OAr)](2) complexes undergo S-S bond cleavage forming monomeric oxosulfido-Mo(VI) species in solution. In the solid state, the 3,5-di-tert-butylphenolate derivative exhibits a centrosymmetric structure, with distorted octahedral anti oxo-Mo(V) centers bridged by a disulfido-kappaS,kappaS' ligand. Hydrolysis of the oxosulfido-Mo(VI) complexes results in the formation of [Tp(i)(Pr)MoO](2)(mu-S(2))(mu-O). In anaerobic solutions, certain oxosulfido-Mo(VI) complexes convert to molybdenyl complexes bearing bidentate 2-mercaptophenolate or related naphtholate ligands formed via intramolecular attack of the sulfido ligand on a coligand C-H group. The oxosulfido-Mo(VI) complexes serve as precursors to biologically relevant Mo(V) and heterobimetallic MoO(mu-S)Cu species and undergo a range of biomimetic reactions. |
Keywords: | Sulfides Molybdenum Organometallic Compounds Mixed Function Oxygenases Models, Molecular |
Rights: | Copyright © 2006 American Chemical Society |
DOI: | 10.1021/ja056109u |
Published version: | http://dx.doi.org/10.1021/ja056109u |
Appears in Collections: | Aurora harvest 5 Chemistry publications Environment Institute publications |
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