Tungsten Bioinorganic Chemistry: Synthesis, Structure, and Reactivity of cis-Oxothiotungsten(VI), cis-Bis(thio)tungsten(VI), and (Ene-1,2-dithiolato)tungsten(IV) Complexes

Synthetic Bioinorganic Chemistry: Scorpionates Turn 50

“…In a similar vein, the active centers in tungsten-containing enzymes such as aldehyde oxidoreductase and formate dehydrogenase [55,56] have been modeled using a variety of Tp RR 0 complexes [52,57], as exemplified by an ene-1,2-dithiolate complex (Fig. 5) described by Young and coworkers [58].…”

Oxidoperoxidotungsten(VI) Complexes with Secondary Hydroxamic Acids: Synthesis, Structure and Catalytic Uses in Highly Efficient, Selective and Ecologically Benign Oxidation of Olefins, Alcohols, Sulfides and Amines with H2O2 as a Terminal Oxidant

“…The interesting aspects of the molecular structure in complexes 2, 4 and 6A are nicely displayed by 1 4 ) are characteristic of peroxido (negative values) and oxido (positive value) complexes with a WO 4+ centre. As the peroxide group is a better σ donor than the oxide group, the metal nuclei are more shielded in peroxido complexes relative to those in oxido complexes containing the same ligands.…”

“…A SUNVIC (U. K.) apparatus was used to measure the melting points of the organic substrates as well as those of their oxidized products. Magnetic susceptibilities were obtained by the Gouy method with Hg[Co(NCS) 4 ] as a standard. Elemental analyses were performed with the help of a Perkin-Elmer 240C elemental analyzer, and the amount of tungsten was estimated gravimetrically as its 8-quinolinolate.…”

“…The key aspect [40,41] of such a reaction is that H 2 O 2 and hydrogen carbonate react in an equilibrium process to produce peroxymonocarbonate, HCO 4 -, which is a more reactive nucleophile than H 2 O 2 and speeds up the epoxidation reaction. Though WO(O 2 ) 2 ·2BMTHAH (also true for BPHAH, BOTHAH, BPTHAH) is not isolable in the present case, it was noted earlier [42] that the corresponding product with QOH as ligand, namely, WO(O 2 ) 2 ·2QOH, was not only isolated, but the attempted crystallization of the QOH adduct afforded the less reactive monoperoxido complex, [WO(O 2 )(QO) 2 ].…”

“…[1] Although the oxygen-transfer property of the MO 2 2+ (M = Mo, W) core is often encountered in biology [2][3][4] and several studies on oxygen-transfer modelling with M = Mo are well-known, [5][6][7][8] the corresponding studies with M = W are relatively sparse. However, several metal complexes containing Mo, [9] W, [10] Mn, [11] Fe [12] and Re [13] have so far been studied as olefin epoxidation catalysts.…”