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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; Donahue, James P; Musgrave, K B; Willer, M W; Nordlander, Ebbe LU ; Hedman, Britt; Hodgson, Keith O and Holm, Richard H (1999) In Inorganic Chemistry 38(18). p.4104-4114
Abstract
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... (More)
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. (Less)
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Contribution to journal
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published
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in
Inorganic Chemistry
volume
38
issue
18
pages
4104 - 4114
publisher
The American Chemical Society
ISSN
1520-510X
DOI
10.1021/ic990440v
language
English
LU publication?
yes
id
1c54a5d9-c8c7-4e3d-99b7-8705fe054dfe (old id 959780)
date added to LUP
2008-08-15 12:03:11
date last changed
2016-04-15 20:35:25
@article{1c54a5d9-c8c7-4e3d-99b7-8705fe054dfe,
  abstract     = {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.},
  author       = {Thapper, Anders and Donahue, James P and Musgrave, K B and Willer, M W and Nordlander, Ebbe and Hedman, Britt and Hodgson, Keith O and Holm, Richard H},
  issn         = {1520-510X},
  language     = {eng},
  number       = {18},
  pages        = {4104--4114},
  publisher    = {The American Chemical Society},
  series       = {Inorganic Chemistry},
  title        = {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},
  url          = {http://dx.doi.org/10.1021/ic990440v},
  volume       = {38},
  year         = {1999},
}