Understanding the Origin of Metal−Sulfur Vibrations in an Oxo-Molybdenum Dithiolene Complex: Relevance to Sulfite Oxidase
2006-02-06T00:00:00Z (GMT) by
X-ray crystallography and resonance Raman (rR) spectroscopy have been used to further characterize (Tp*)MoO(qdt) (Tp* is hydrotris(3,5-dimethyl-1-pyrazolyl)borate and qdt is 2,3-quinoxalinedithiolene), which represents an important benchmark oxomolybdenum mono-dithiolene model system relevant to various pyranopterin Mo enzyme active sites, including sulfite oxidase. The compound (Tp*)MoO(qdt) crystallizes in the triclinic space group, P1̄, where a = 9.8424 (7) Å, b = 11.2323 (8) Å, c = 11.9408 (8) Å, α = 92.7560 (10)°, β = 98.9530 (10)°, and γ = 104.1680 (10)°. The (Tp*)MoO(qdt) molecule exhibits the distorted six-coordinate geometry characteristic of related oxo-Mo(V) systems possessing a single coordinated dithiolene ligand. The first coordination sphere bond lengths and angles in (Tp*)MoO(qdt) are very similar to the corresponding structural parameters for (Tp*)MoO(bdt) (bdt is 1,2-benzenedithiolene). The relatively small inner-sphere structural variations observed between (Tp*)MoO(qdt) and (Tp*)MoO(bdt) strongly suggest that geometric effects are not a major contributor to the significant electronic structural differences reported for these two oxo-Mo(V) dithiolenes. Therefore, the large differences observed in the reduction potential and first ionization energy between the two molecules appear to derive primarily from differences in the effective nuclear charges of their respective sulfur donors. However, a subtle perturbation to Mo−S bonding is implied by the nonplanarity of the dithiolene chelate ring, which is defined by the fold angle. This angular distortion (θ = 29.5° in (Tp*)MoO(qdt); 21.3° in (Tp*)MoO(bdt)) observed between the MoS2 and S−CC−S planes may contribute to the electronic structure of these oxo-Mo dithiolene systems by controlling the extent of S p−Mo d orbital overlap. In enzymes, the fold angle may be dynamically modulated by the pyranopterin, thereby functioning as a transducer of vibrational energy associated with protein conformational changes directly to the active site via changes in the fold angle. This process could effectively mediate charge redistribution at the active site during the course of atom- and electron-transfer processes. The rR spectrum shows bands at 348 and 407 cm-1. From frequency analysis of the normal modes of the model, [(NH3)3MoO(qdt)]1+, using the Gaussian03 suite of programs, these bands are assigned as mixed-mode Mo−S vibrations of the five-membered Mo-ditholene core structure. Raman spectroscopy has also provided additional evidence for an in-plane pseudo-σ dithiolene S−Mo dxy covalent bonding interaction in (Tp*)MoO(qdt) and related oxo-Mo-dithiolenes that has implications for electron-transfer regeneration of the active site in sulfite oxidase involving the pyranopterin dithiolene.