Molybdenum complexes spectroscopy

Spatially resolved Raman spectroscopy has provided insights into the physicochemical processes that determine the distribution of the H2PMoOi iCoOV active phase in alumina pellets (Bergwerff et al., 2005). Molybdenum and cobalt complexes were found to diffuse through the pore structure of the alumina pellets at different rates the transport of cobalt complexes was fast, whereas molybdenum complexes required several hours to reach an equilibrated distribution. Spatially resolved Raman monitoring provides information about how preparation conditions affect the distribution of molybdenum ions (Bergwerff et al., 2005). 

It is obvious that x-ray cyrstallographic methods will be the final arbiter of the structural features of molybdoproteins, but until such structures are obtained, and even afterwards as far as dynamic features are concerned, spectroscopic methods must be used to gain insight into the nature of these catalysts. Electronic spectroscopy so far has been of little use here since molybdenum complexes in general appear to exhibit broad weak absorptions. In proteins these are always buried under absorptions from hemes, flavins, and iron-sulfur centers. Massey et al., (15) discovered that pyrazolo [3,4-d] pyrimidines will bind Mo (IV) in milk xanthine oxidase that had been reduced with xanthine... 

As yet, no X-ray crystal structures are available for any of the molybdenum enzymes in Table I. Therefore, present descriptions of the coordination environment of the molybdenum centers of the enzymes rest primarily upon comparisons of the spectra of the enzymes with the spectra of well-characterized molybdenum complexes. The two most powerful techniques for directly probing the molybdenum centers of enzymes are electron paramagnetic resonance (EPR) spectroscopy and X-ray absorption spectroscopy (XAS), especially the extended X-ray absorption fine structure (EXAFS) from experiments at the Mo K-absorption edge. Brief summaries of techniques are presented in this section, followed by specific results for sulfite oxidase (Section III.B), xanthine oxidase (Section III.C), and model compounds (Section IV). 

The amido nitrosyl molybdenum complex MoCI(Tp )(NO)-(NH2)] reacts with alcohols, yielding the bisalkoxo complexes [Mo(OR)2(Tp )(NO)] (R = Me, Et, "Pr, Bu), analyzed by IR and H-NMR spectroscopy.60 Topaloglu and McCleverty also reported the synthesis and characterization of amido- and amido(monoalkylamido)-Mo(Tp )(NO) species61 and of [MoCl-(Tp )(NO)(OC6H4PPh 2-p)].62... 

Various kinds of the theoretical spectroscopies for the transition metal complexes were also reviewed. For the excitation spectrum of Cr02Cl2, the SAC-Cl method simulated accurate spectrum. For tetraoxo metal complexes, the systematic studies explained the spectral differences when the central metal was substituted. In the analysis of the NMR chemical shift, not only the optically allowed states but also the magnetically allowed states are important. In the molybdenum complexes, the inverse of the d-d excitation energy is proportional to the experimental chemical shift. The photofragmentation reaction of Ni(CO)4 was also studied and the reaction mechanism was clarified. 

Jonas and co-workers have pointed out that often a compromise must be found between sensitivity and resolution in NMR spectroscopy [76]. Line narrowing is optimum in regions of low supercritical fluid density (where the viscosity is low), but then the solubility of compounds is also low. Sometimes, admixtures with small amounts of low-viscosity solvents such as acetone may be tried to obtain a reasonable concentration of the compounds studied, i.e. coordination compounds such as (R-N=CH)2Mo(CO)4. However, line widths for this compound decrease by a factor of about four to six when comparing benzene-dg solutions to supercritical CO2 (with 8% acetone-de). The dispersion of the nitrogen chemical shift ensures identification of coordinated ligands by using NMR, in the above molybdenum complex, where A5( n) = -36 ppm) [75]. 

With chromium, molybdenum, and tungsten carbonyls, 1 and 2 displace two CO molecules and form the trans complexes, (l)2M(CO)4 and (2)2M(CO)4 (M = Mo, Cr and W). As an example, the structure of (l>2Cr(CO)4 is shown in Fig. 6. To provide a measure of the strength of these ligands as electron donors, the C=0 stretching frequencies for these complexes were determined by IR spectroscopy [9]. The frequencies for the molybdenum complexes, and for a number of isostmctural Mo compounds, are shown in Table 1. The data indicate that toward Mo(CO)4 as a reference acid, 1 is about equal to triphenylphosphine in donor ability, whUe 2 is slightly weaker, more resembling a trialkoxyphosphine. The stable carbene isostmctural with 1 is an extremely powerful Lewis base toward molybdenum, however, surpassing even trialkylphosphines. 

---