Syntheses, Spectroscopy, and Redox Chemistry of Encapsulated Oxo−Mo(V) Centers:  Implications for Pyranopterin-Containing Molybdoenzymes

Abstract

Coordination by at least four sulfur donors to an embedded molybdenum center has been found to be a common feature in the crystal structures of many mononuclear molybdenum enzymes. In an effort to model embedded molybdenum centers, we have synthesized dendritic thiolate ligands and their oxo-molybdenum complexes containing a [Mo(V)OS(4)](-) core. These compounds have been isolated in pure form as blue solids or gummy materials, and the molecular nature of these compounds has been confirmed by electrospray ionization mass spectrometry and infrared, electron paramagnetic resonance, and UV-vis spectroscopies. The dendritic complexes exhibit little variation in their broad S --> Mo charge transfer band (lambda(max) approximately 600 nm; epsilon approximately 6000 M(-)(1) cm(-)(1)), Mo=O vibration energy (941-943 cm(-)(1)), and EPR g-values (g( parallel ) approximately 2.02; g( perpendicular ) approximately 1.98; g(av) approximately 1.99). The spectroscopic data confirm the integrity of the square pyramidal [Mo(V)OS(4)](-) core with little geometric distortions, suggesting that the electronic structure at the metal center is not perturbed by the ligand architecture. The electronic structure of these complexes, calculated by the density functional theory, demonstrates a similar composition of the HOMO. In complexes 6 and 7a, the energy of the HOMO orbital might be modulated by the difference in the electronic structure of the ligands. The Mo(V/IV) reduction potentials vary as a function of the dielectric constant and the donor number of the solvent. The kinetics of the reduction is influenced by the reorganization of the geometry and the encapsulating effect. We suggest that protein structure imposed microenvironments may control the dielectric properties and hence the redox properties of the metal center in many metallobiomolecules.

Solution, Solid, and Gas Phase Studies on a Nickel Dithiolene System: Spectator Metal and Reactor Ligand

“…81 The second factor can be viewed as a perturbation that arises from the solvation of the redox center as well as specific ion-pairing. 82 The solvation components are important in the event that the redox center in the molecule is differentially affected than other parts of the molecules such as in a dendrimer encapsulated redox center. 82 - 88 However, in the present case the salvation component is expected to be less significant in dictating the difference in the redox potentials.…”

Nitrate and periplasmic nitrate reductases

“…This alteration in covalency along with a change in the dielectric properties alters the reduction potential of the molybdenum center, thus providing the driving force of the reaction. 142,143 …”

Photoelectron Spectroscopy of the Doubly-Charged Anions [MIVO(mnt)2]2- (M = Mo, W; mnt = S2C2(CN)22-): Access to the Ground and Excited States of the [MVO(mnt)2]- Anion

“…23,24 The electronic structures of a range of [Mo V OS 4 ] -(d 1 ) species (S 4 ) tetrathiolato, bis(dithiolato), or bis(dithiolene)) have been investigated by a combination of physical and theoretical techniques. [25][26][27][28][29][30][31][32] Intense low-energy transitions in electronic spectra are proposed to involve charge transfer from molecular orbitals of predominantly ligand sulfur character to the highest occupied molecular orbital (HOMO), which is metal-based and essentially nonbonding. [27][28][29][30][31] Photodetachment photoelectron spectroscopy (PES) allows detailed investigation of the electronic structure of gaseous species.…”