Equency calculation in the transition state (only 1 imaginary frequency) to make sure that the pathway connects the transition state to each the reactant and product.3. Outcomes AND Analysis 3.1. Electronic Structures. 3.1.1. S K-Edge XAS Information. The sulfur K-edge XAS spectra for the monooxo MoIV and bisoxo MoVI bis-dithiolene complexes are shown in Figure 2. The spectra of your [MoIV(OSi)(bdt)2]- and [MoVIO(OSi)(bdt)2]- complexes are also incorporated for reference. The [MoIVO(bdt)2]2- complicated (Figure 2A) features a dominant feature at2. EXPERIMENTAL SECTION2.1. Sample Preparation. The [Mo IV O(bdt) two ] 2- and [MoVIO2(bdt)2]2- complexes had been prepared as inside the literature.27 two.two. S K-Edge XAS Information Collection and Evaluation. All sulfur Kedge XAS information have been measured in the Stanford Synchrotron Radiation Lightsource (SSRL) applying the 54-pole wiggler beamline 6-2 operating in high field mode of ten kG using a Ni-coated harmonic rejection mirror plus a totally tuned Si(111) crystal monochromator. Details from the beamline configuration are provided in ref 25. The solid samples had been ground into fine powders in an inert atmosphere (N2) dry glovebox exactly where the O2 level was less than 1 ppm and dispersed as thinly as you can on Mylar tape to decrease prospective self-absorption. A 6 mthick, sulfur-free polypropylene front window was employed to prevent sample exposure to air upon mounting within the sample box. The photon power was calibrated to the maximum of your initial pre-edge function of Na2S2O3?H2O at 2472.02 eV. A total of 3-5 scans had been measured for every sample to ensure reproducibility. Raw data have been calibrated and averaged using MAVE in the EXAFSPAK application package.28 With all the use from the PySpline plan,29 the background was removed from all spectra by fitting a second-order polynomial to the pre-edge area and subtracting it in the whole spectrum.201286-95-5 site Normalization with the data was accomplished by fitting a flat second-order polynomial or straight line towards the post-edge region and normalizing the edge jump to 1.103883-30-3 web 0 at 2490.PMID:23329650 0 eV.24 Since the post-edge region also consists of intensity in the Mo L3-edge, the information had been further scaled such that the area in between the S K-edge and Mo L3-edge had the identical intensity as the corresponding area of a tungsten dithiolene complicated.10 The error from background subtraction and normalization is much less than 1 . Intensities of the pre-edge functions have been obtained by fitting the spectra with peaks possessing pseudo-Voigt line shape peaks with 1:1 Lorentzian to Gaussian contributions, using the EDG_FIT program.28 The reported intensity values have been based around the typical of 10-12 superior fits. The intensities of your S 1s C-S */* transitions at 2473.8 eV were based on previously published values for similar complexes,ten exactly where these edge functions have been greater resolved, enabling for ?0 variation from the intensities and peak widths. The error in the fitting process was much less than 10 . The fitted intensities were converted to S 3p character making use of eq 1, exactly where D0 could be the peak region and also the value of Is was set at 14.1,10 exactly the same as previously published final results for equivalent complexes. 2.three. DFT Calculations. DFT calculations had been performed using the Gaussian 09 package30 with each the pure functional BP86 (Becke GGA exchange with Perdew 1986 nonlocal correlation31,32) along with the hybrid functional B3LYP (Becke GGA exchange including 20Figure 2. S K-edge XAS spectra of (A) [MoIVO(bdt)2]2-, (B) [MoIV(OSi)(bdt)2]-, (C) [MoVIO2(bdt)2]2-, and (D) [MoVIO(OSi)(bdt)2]-.dx.doi.org/.