Oxo–tungsten bis-dithiolene complexes relevant to tungsten centres in enzymes

The Electronic Structure and Spectroscopy of Metallo‐Dithiolene Complexes

“…[Adapted from (16).] research has focused on how simple variations in the donor ability of a coordinated dithiolene affect the reduction (7,8,20,22) and ionization potentials of oxo-molybdenum dithiolenes. Photoelectron spectroscopy has revealed that the Mo d xy redox orbital of (L-N 3 )MoO(qdt) is stabilized by $0.8 eV compared to that of (L-N 3 )MoO(tdt) (20,22).…”

Sulfur K-edge XAS of WVO vs. MoVO bis(dithiolene) complexes: Contributions of relativistic effects to electronic structure and reactivity of tungsten enzymes

“…First, E o W < E o Mo for strictly analogous redox couples, with potential differences decreasing as bond covalency increases [6,[9][10][11][12][13][14]. Second, in Mo/W enzymes and Mo/W isostructural complexes, oxo transfer from substrate to metal (M IV → M VI ) is faster with tungsten [6,9,[15][16].…”

Photoconducting Devices with Response in the Visible–Near-Infrared Region Based on Neutral Ni Complexes of Aryl-1,2-dithiolene Ligands

“…One of the most frequently encountered synthetic procedures consists of reacting α-halo-ketones with alkylxanthate anions to give the corresponding α-ketoxanthate esters, which give the relevant vinylene dithiocarbonates in strongly acidic media (Scheme 1). 45,78 Following this route, the 4-phenyl-and 4-(2-naphtyl)- [1,3]dithiol-2-ones were synthesized as previously described 48,49 (see details on the X-ray diffraction analysis of 4-phenyl- [1,3]dithiol-2-one in Table S1 and Figure S1). Complexes S1 and Figure S2 and Figure 1, respectively), the latter being isostructural to the corresponding gold(III) complex, 48 show the central metal ion coordinated in a square-planar fashion, with the ligands assuming trans and cis conformations, respectively, and the aryl substituents twisted with respect to the dithiolene core by 18.6(2)/18.1(2) and 26.7(6)/26.9(7) °, respectively.…”