0000000000255682
AUTHOR
Pedro Palanca
Modeling for the active site nitrate reductase. Oxidation of the complex [MovO(O2CC(S) CH3Ph)2]− by nitrate and nitrite in methanol
Abstract Under acid conditions the [MoVIO2(O2CC(S)CH1Ph)2]2 reacts with thiols to yield the monomeric [MoVO(O2CC(S)CH3Ph)2] and disulfide. The reduced complex [MoVO(O2CC(S)CH3Ph)2]− can react with NO3− and NO2− in a one-electron step yeilding respectively NO2 and NO and the original molybdenum (VI)-dioxo complex. The experimental pseudo-first-order rate constant with respect to the Mo(V) complex at 25°C was found to be kobs=2.3×10−4s−1 for NO3− and kobs=1.0×10−2 for NO2−. Oxo transfers to and from the substrate have been coupled to produce a catalytic system which turns over the reaction RSH+(No3− or NO2−)+H+a 1 2 [ RS ] 2 +( NO ] 2 or NO )+ H 2 O , in which thiols, NO1− and NO2− serve as a…
Polymer-supported molybdenyl thioglycolate as oxygen atom transfer reagent
Abstract Oxo-transfer reactions of a variety of substrates in DMF or methanol using polymer-supported molybdenyl thioglycolate (PSMT) have been investigated. The clean oxidation of Me 2 PhP, n -butanethiol or benzoin to yield Me 2 PhPO, disulfide or benzil, respectively, occurs in high yield. In the presence of air or pyridine N-oxide, a catalytic cycle is accomplished which goes on until the completion of the substrate.
Synthesis and characterization of molybdenum(VI)-dioxo complexes containing both coordinated thiolate and carboxylate groups. Reactions with their own free ligands
Abstract The synthesis, characterization and spectroscopic properties of a group of Mo(VI) complexes having thiocarboxylate ligands of type [MoVIO2(O2CC(S)MePh-X)2]2 have been reported (X = H, p-Me, p-Cl). The peak potential for the Mo(VI) reduction increasing according to the electron-donor ability of X (Me > H > Cl). Reaction of these Mo(VI) complexes with their own free ligands has been studied by ESR and UV-Vis spectroscopy, yielding the monomeric [MoVO(O2CC(S)MePh-X)2]− as unique complex products. The kinetic study of this oxidation reaction has also been investigated.
[MoO2(SCPh2CO2)2]2− and [MoO(SCPh2CO2)2]− anion complexes. A theoretical structure characterization
Abstract Geometry optimization of [MoO 2 (SCH 2 CO 2 ) 2 ] 2− and [MoO(SCH 2 CO 2 ) 2 ] − systems as models of [MoO 2 (SCPh 2 CO 2 ) 2 ] 2− and [MoO(SCPh 2 CO 2 ) 2 ] − anion complexes have been carried out at STO-3G, 3-21G, LANL1MB and LANL2DZ basis set levels. A comparison of the theoretical results and X-ray experimental data has been performed. STO-3G minimal basis set produces the best geometrical agreement, in particular the distances and orientations of the different ligands linked to molybdenum transition metal. A large structural overlap with STO-3G optimized geometry and X-ray data has been found for the [MoO 2 (SCPh 2 CO 2 ) 2 ] 2− and [MoO(SCPh 2 CO 2 ) 2 ] − anion complexes.
Molybdenum(VI)-dioxo complexes with sterically bulky thiocarboxylate ligands. Reactions with aliphatic thiols and electrochemical properties
Abstract Under acid conditions, the reaction of (Bu n 4 N)2[Mo VI O 2 (O 2 CC(S)Ph 2 ) 2 ] with aliphatic thiols yields the monomeric [Mo V O(O 2 CC(S)Ph 2 ) 2 ] − as unique complex product. The experimental pseudo-first order rate constant with respect to the Mo(VI) complex was found to be K =6.1 × 10 −5 s −1 . At neutral pH, however, an unstable Mo(IV) species was formed which was also electrochemically detected in a reversible Mo(V,IV) couple. [Mo V O(O 2 CC(S)Ph 2 ) 2 ] − appears to be obtained by the reaction of [Mo IV O(O 2 CC(S)Ph 2 ) 2 ] 2− with unreacted [Mo VI O 2 (O 2 CC(S)Ph 2 ) 2 ] 2− . Steric features on the ligand (gemdiphenyl groups) explain that the latter reaction does not…
Oxygen atom transfer reaction involving oxomolybdenum complexes with sterically bulky thiocarboxylate ligands and biochemical interesting substrates in methanol at neutral pH
Abstract Oxidation–reduction reactions of substrates in systems containing the complex [Mo VI O 2 (O 2 CC(S)CH 3 Ph) 2 ] 2− in methanol have been investigated as models of oxo-transfer reactions. At neutral pH, the [Mo VI O 2 (O 2 CC(S)CH 3 Ph) 2 ] 2− reacts with Me 2 PhP or n -butanethiol to yield a [Mo IV O(O 2 CC(S)CH 3 Ph) 2 ] 2− species and Me 2 PhPO or disulfide, respectively. The Mo IV O complex reduces a variety of substrates XO = Me 2 SO and pyridine N-oxide conducing formation of X = Me 2 S and pyridine. The occurrence of these reactions produces a catalytic system Me 2 PhP + XO → Me 2 PhPO + X and 2BuSH + XO → [BuS] 2 + X + H 2 O. In this work we have also included the study of …
Preparation of 4-substituted 1,3-oxathiolan-5-onesviathe sulphenium ion intermediate generated by the pummerer rearrangement
4-Substituted 1,3-oxathiolan-5-ones have been synthesized via the Pummerer rearrangement from the S-oxide of the parent molecule. The 4,5-dione is obtained in the presence of pyridine N-oxide.