Es. These have drastically assisted in creating an understanding on the mechanisms of oxo transfer to MoIV and oxo transfer from MoVIO2.9 A number of experimental and theoretical research have focused on DMSO reductase reactions to understand the geometric and electronic structural contributions to function. 10-15 Our preceding study of [MoIV(OSi)(bdt)2]- and [MoVIO(OSi)(bdt)2]- complexes (OSi = [OSiPh2tBu]-, bdt = benzene-1,2-dithiolate(2-), Figure 1B,D), offered the following insight into the nature in the DMSO oxo transfer reaction:10 (1) the dithiolene ligands are innocent (i.e., not redox-active), but are strong -donors that stabilize the singlet ground state of the MoIV within the absence of a strong oxo ligand; and (2) inside the oxo transfer from the DMSO to the MoIV center, the S-O bond elongation polarizes the bond, and decreases the power gap involving frontier molecularReceived: April 10, 2014 Published: June 2,dx.doi.org/10.1021/ja503316p | J. Am. Chem. Soc. 2014, 136, 9094-Journal of the American Chemical SocietyArticleFigure 1. Crystal and geometry optimized structures in the complexes in this study. Bond distances in angstroms (? are listed below the structure. Mo-S* indicates the sulfur atom that is certainly trans-axial to the oxo ligand. In panel D, comparable Mo-S bond distances had been averaged.orbitals (FMOs, the LUMO on the substrate plus the HOMO occupied d-orbital on the MoIV), enabling the transfer of the electron pair from Mo to the substrate to finish the oxo transfer. There have also been a variety of sulfite oxidase model research. Holm and co-workers have synthesized a model that matched the native enzyme structure properly, but there was no reported reactivity.16 The Sarkar group measured the kinetics of oxo transfer from [MoVIO2(mnt)2]2- (mnt = maleonitriledithiolate(2-)) to HSO3- and identified Michaelis-Menten kinetics.17 Other model research focused on the transfer of an oxo group from a MoVIO2 species to phosphine substrates.5-Oxaspiro[2.4]heptane-1-carboxylic acid Order Hall and co-workers studied the reaction: [MoVIO2(tBuL-NS)2] + PMe3 [MoIVO(tBuL-NS)2] + OPMe3 computationally18 according to the experimental data of Holm an co-workers on this reaction.Methyl 4-bromo-6-methoxypicolinate supplier 19 The tBuL-NS ligand had nonconjugated nitrogen and sulfur groups bound towards the Mo.PMID:24360118 Basu and co-workers20 studied the reaction: [LiPrMoO2(OPh)] + PMe3 [LiPrMoO(OPh)-Solvent] + OPMe three both experimentally and computationally, where LiPr is usually a tridentate ligand with nitrogens bound to Mo.20 Neither study utilized the dithiolene ligation present within the enzymes. You’ll find also research to evaluate electronic structures of model complexes that do not have oxo transfer reactivity, but include dithiolene ligation.21,22 The Holm group has synthesized a series of MoIVO and MoVIO2 bisdithiolene complexes, characterized their geometric structures and showed that they undergo oxo transfer to phosphite esters with well determined kinetics parameters for the reaction[Mo VIO2 (mnt)2 ]2 – + P(OMe)three [MoIV O(mnt)two ]2 – + OP(OMe)The focus in the existing study is to use spectroscopic and computational strategies to ascertain the electronic structure of those Mo dithiolene complexes, and use experimentally calibrated calculations to evaluate this oxo transfer reaction. The aim is usually to understand this and the other oxo transfers to substrate on a molecular level and to examine these to the reaction coordinate obtained for DMSO reductase, which involves oxo transfer from substrate to MoIV. In our preceding study with the DMSO reductase reaction, S Kedge X-ray absorpti.
