Mononuclear Sulfido-Tungsten(V) Complexes: Completing the Tp*MEXY (M = Mo, W; E = O, S) Series.

Orange Tp*WSCl has been synthesized from the reactions of Tp*WOCl with boron sulfide in refluxing toluene or Tp*WSCl with PPh in dichloromethane at room temperature. Mononuclear sulfido-tungsten(V) complexes, Tp*WSXY {X = Y = Cl, OPh, SPh, SePh; X = Cl, Y = OPh; XY = toluene-3,4-dithiolate (tdt), quinoxaline-2,3-dithiolate (qdt); and Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate} were prepared by metathesis of Tp*WSCl with the respective alkali metal salt of X/XY, or [NHEt](qdt). The complexes were characterized by microanalysis, mass spectrometry, electrochemistry, and infrared (IR), electron paramagnetic resonance (EPR) and electronic absorption spectroscopies.

Paramagnetic oxotungsten(V) complexes containing the hydrotris(3,5-dimethylpyrazol-1-yl)borate ligand.

Sky-blue Tp*WOCl(2) has been synthesized from the high-yielding reaction of Tp*WO(2)Cl with boron trichloride in refluxing toluene. Dark-red Tp*WOI(2) was prepared via thermal decarbonylation followed by aerial oxidation of Tp*WI(CO)(3) in acetonitrile. From these precursors, an extensive series of mononuclear tungstenyl complexes, Tp*WOXY [X = Cl(-), Y = OPh(-), SPh(-); X = Y = OPh(-), 2-(n-propyl)phenolate (PP(-)), SPh(-), SePh(-); XY = toluene-3,4-dithiolate (tdt(2-)), quinoxaline-2,3-dithiolate (qdt(2-)), benzene-1,2-diselenolate (bds(2-)); Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate], was prepared by metathesis with the respective alkali-metal salt of X(-)/XY(2-) or (NHEt(3))(2)(qdt).

Synthesis, characterization, and biomimetic chemistry of cis-oxosulfidomolybdenum(VI) complexes stabilized by an intramolecular Mo(O)=S...S interaction.

The reactions of jade-green Tp*MoIVO(S2PR2) [Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate; R = Et, Pri, Ph] with propylene sulfide produce ochre-red Tp*MoVIOS{SP(S)R2}. The complexes have been characterized by microanalysis, mass spectrometry, cyclic voltammetry, spectroscopy (IR, NMR, UV-vis, and X-ray absorption), and X-ray crystallography. The distorted-octahedral isopropyl and phenyl derivatives feature a tridentate fac-Tp* ligand, a terminal oxo ligand, and a unique five-membered Mo(=S){SP(=S)R2 ring moiety formed by a weak, intramolecular, bonding interaction between the Mo=S1 and (uncoordinated) S3=P moieties.

Redox interplay of oxo-thio-tungsten centers with sulfur-donor co-ligands.

The oxo-thio-W(VI) complexes TpWOS(S(2)PR(2)-S) and TpWOS(pyS-S) (Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate, R = OEt, Ph; pyS = pyridine-2-thiolate) have been prepared and characterized by microanalytical, spectroscopic, and structural techniques. Crystals of the 1,2-dichloroethane hemisolvate of TpWOS(S(2)PPh(2)-S) belong to the triclinic space group Ponemacr; with a = 10.732(6) A, b = 16.