0000000000255682
AUTHOR
Pedro Palanca
showing 7 related works from this author
Modeling for the active site nitrate reductase. Oxidation of the complex [MovO(O2CC(S) CH3Ph)2]− by nitrate and nitrite in methanol
1998
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
2000
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 ow…
1998
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
1995
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
1991
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 …
1999
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
1993
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.