Sökning: WFRF:(Hodgson Keith)
> (1999) >
The Unperturbed Oxo...
The Unperturbed Oxo-Sulfido Functional Group cis-Mo(VI)OS, Related to that in the Xanthine Oxidase Family of Molybdoenzymes: Synthesis, Structural Characterization and Reactivity Aspects
-
Thapper, Anders (författare)
-
Donahue, James P (författare)
-
Musgrave, K B (författare)
-
visa fler...
-
Willer, M W (författare)
-
- Nordlander, Ebbe (författare)
- Lund University,Lunds universitet,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
-
Hedman, Britt (författare)
-
Hodgson, Keith O (författare)
-
Holm, Richard H (författare)
-
visa färre...
-
(creator_code:org_t)
- 1999-08-20
- 1999
- Engelska.
-
Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 1520-510X .- 0020-1669. ; 38:18, s. 4104-4114
- Relaterad länk:
-
http://dx.doi.org/10...
-
visa fler...
-
https://lup.lub.lu.s...
-
https://doi.org/10.1...
-
visa färre...
Abstract
Ämnesord
Stäng
- The oxo-sulfido functional group cis-MoVIOS is essential to the activity of the xanthine oxidase family of enzymes but has proven elusive to synthesis in molecules containing no other four-electron ligands. A direct route to molecules containing this group has been achieved. The reaction system [MoO2(OSiPh3)2]/L in dichloromethane yields the complexes [MoVIO2(OSiPh3)2L] (L = phen (1), Me4phen (2), 4,4'-Me2bpy (3), 5,5'-Me2bpy (4), 2 py (5)) (74-96%), which are shown to have a distorted octahedral structure of crystallographically imposed C2 symmetry (1, 5) with cis oxo and trans silyloxy ligands. The related reaction system [MoO3S]2-/2Ph3SiCl/L in acetonitrile affords the complexes [MoVIOS(OSiPh3)2L] (L = phen (6), Me4phen (7), 4,4'-Me2bpy (8), 5,5'-Me2bpy (9)) (36-69%). From the collective results of elemental analysis, mass spectrometry, 1H NMR, and X-ray structure determinations (6, 7), complexes 6-9 are shown to contain the cis-MoVIOS group in molecules with the same overall stereochemistry as dioxo complexes 1-5. The crystal structures of 6 and 7 exhibit O/S disorder, which was modeled in refinements with 50% site occupancies. The Mo=O (1.607(5) (6), 1.645(5) (7) Å) and Mo=S (2.257(3) (6), 2.203(2) (7) Å) bond distances obtained in this way are somewhat shorter and longer, respectively, than expected. Distances obtained by molybdenum EXAFS analysis using the GNXAS protocol for 6-9 (Mo=O 1.71-1.72 Å; Mo=S 2.18-2.19 Å) are considered more satisfactory and are in good agreement with EXAFS values for xanthine oxidase. Molybdenum K-edge data for 1 and 6-9 are reported. Reaction of 7 with Ph3P in dichloromethane results in sulfur abstraction and formation of [MoVOCl(OSiPh3)2(Me4phen)] (10), which has a distorted octahedral structure with cis O/Cl and cis silyloxy ligands. Sulfur rather than oxygen abstraction is favored by relative Mo=O/Mo=S bond strengths. Complexes 6-9 should allow exploration of the biologically significant cis-MoVIOS group.
Ämnesord
- NATURVETENSKAP -- Kemi -- Oorganisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)
Publikations- och innehållstyp
- art (ämneskategori)
- ref (ämneskategori)
Hitta via bibliotek
Till lärosätets databas