Publisher Summary This chapter presents a discussion on the bioinorganic chemistry of pterin-containing molybdenum and tungsten enzymes. The chapter focuses on the current results and the interplay of model and enzyme chemistry. Attention is directed to sulfite oxidase and xanthine oxidase, the archetypal examples of molybdenum enzymes, containing, respectively, dioxo-Mo(VI) and oxo-thio-Mo(VI) oxidized centers. Biochemical and model studies of molybdopterin, Mo-co, and related species are described in this chapter. A brief survey on the physical and spectroscopic techniques employed in the study of the enzymes is presented and their impact on the current understanding of the coordination about the molybdenum atom in sulfite oxidase and xanthine oxidase is discussed. Structural and spectroscopic models are also presented in the chapter. The chapter also explains the xanthine oxidase cycle and facets of intramolecular electron transfer in molybdenum enzymes. The pterin-containing tungsten enzymes and the evolving model chemistry are discussed. Current descriptions of the coordination environment of the molybdenum centers of the enzymes rest primarily upon the comparisons of the spectra of the enzymes with the spectra of well-characterized molybdenum complexes. The unexpected discovery that several hyperthermophilic organisms possess pterin-containing tungsten enzymes promises to stimulate the development of oxo-thio-tungsten chemistry.

Bioinorganic chemistry of pterin-containing molybdenum and tungsten enzymes

Oil-soluble MO-S compounds as lubricant additives

A new wet chemistry approach, based on the hot-injection–thermolytic decomposition of the single-source precursor [Mo2O2S2(S2COEt)2] in oleylamine, is described for the production of nanodimensional 1H-MoS2@oleylamine. High quality freestanding MoS2 nanosheets capped with oleylamine have been prepared and subjected to detailed compositional analyses for the first time. The selection of the appropriate reaction temperatures (200–325 °C) in the simple yet robust procedure allows control of the lateral nanosheet dimensions which range from 4.5 to 11.5 nm, as 1H-MoS2@oleylamine entities which maintain a consistent chemical composition (MoS2·oleylamine0.28–0.33). This work provides the first example of atomic resolution STEM imaging of these fine-scale nanosheet materials, providing new insights into their morphology and demonstrating that those freestanding MoS2 nanosheets are pure, highly crystalline, randomly oriented monolayers. The 1H-MoS2@oleylamine samples were analyzed by attenuated total reflectance F...

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Synthesis of Lateral Size-Controlled Monolayer 1H-MoS2@Oleylamine as Supercapacitor Electrodes.

The Coordination and Bioinorganic Chemistry of Molybdenum

Homonuclear and heteronuclear oxo-bridged compounds of the transition elements

Preparation and characterization of two series of dimeric molybdenum(V) N,N-dialkyldithiocarbamates. Their interrelation and chemistry as a model for the active site of nitrogenase

John E. Searles

Papers

Preparation and characterization of two series of dimeric molybdenum(V) N,N-dialkyldithiocarbamates. Their interrelation and chemistry as a model for the active site of nitrogenase