Trithiotungsten(VI) Complexes Having Phosphine-Thiolate Hybrid Ligands:  Synthesis and Cluster Forming Reactions with CuBr, FeCl₂, and [Fe(CH₃CN)₆](ClO₄)₂

Abstract

Five-coordinated trithiotungsten complexes (PPh(4))[(dmsp)W(S)(3)] (1a) and (PPh(4))[(dpsp)W(S)(3)] (1b) (R(2)PCH(2)CH(2)S(-); R = Me (dmsp-)), Ph (dpsp-))) were synthesized by addition of Hdmsp and Hdpsp to a THF solution of (PPh(4))[(EtS)W(S)(3)]. Treatment of 1a with CuBr in the presence of PPh(3) in CH(3)CN afforded a WCu(2) cluster (dmsp)WS(3)Cu(2)(PPh(3))(2)Br (2). The reaction of 1a with 1 equiv of FeCl(2) went smoothly to generate a 1:1 adduct (PPh(4))[(dmsp)WS(3)(FeCl(2))] (3), while 3 did not react further with excess FeCl(2). On the other hand, 3 was found to react with [Fe(CH(3)CN)(6)](ClO(4))(2), giving rise to an unusual tetranuclear cluster, [(dmsp)WS(3)](2)Fe(2)Cl (4), while the reaction of 1a with 2 equiv of [Fe(CH(3)CN)(6)](ClO(4))(2) led to a cyclic octanuclear cluster [(dmsp)WS(3)Fe](4) (5). Although the oxidation states of W(VI), Cu(I), and Fe(II) are retained in 2 and 3, reduction of the metal ions occurs in the formation of 4 and 5. All the complexes reported in this paper were structurally characterized by X-ray analysis. It is anticipated that the new type of trithiotungsten complexes, 1a and 1b, will serve as potential synthons for various heterometallic sulfide clusters.

Selenium as a Structural Surrogate of Sulfur: Template-Assisted Assembly of Five Types of Tungsten–Iron–Sulfur/Selenium Clusters and the Structural Fate of Chalcogenide Reactants

“…The η 2 binding mode of the WS 3 group has been previously observed with the heavier Group 8–10 metals. 21 The dimensions of the WS 2 Fe rhomb are nearly the same as in related molecules such as [S 2 WS 2 FeX 2 ] 2− (X = anion) 34–36 and [(Me 2 PCH 2 CH 2 S)W(S)S 2 FeCl 2 ] 1−37 The product is best considered as W 6+ Fe 2+ with the isomer shift of 0.52 mm/s, relative to an FeS 4 site, apparently decreased by some extent of electron delocalization to the fully oxidized tungsten site. Reaction with two equiv each of FeCl 2 and NaSEt produces trinuclear 3 38 (61%) which undergoes ligand substitution reaction 4 to yield isostructural 4 (49%) whose isomer shift of 0.45 mm/s suggests the description W 4+ Fe 3+ Fe 2+ .…”

Nucleophilic Reactivity and Oxo/Sulfido Substitution Reactions of MVIO3Groups (M = Mo, W)

“…They contain the M VI S 3 group, which with M = Mo is precedented only by [Cp*MoS 3 ] - in five- and six-coordinate complexes. (Two non-oxo tetrahedral species containing the Mo VI S 3 group have also been described. , ) Complex 18 is most closely related to [(Tp*)WS 3 ] - ; several other examples of the W VI S 3 group have been reported. ,,, None of these compounds were prepared by oxo/sulfido substitution. A heterogeneous reaction between 14 and excess (5.5:1 mol ratio) of B 2 S 3 in acetonitrile for 4 days followed by chromatography afforded the yellow oxodisulfido complex 20 .…”

“…45,50 ) Complex 18 is most closely related to [(Tp*)WS 3 ] -; 51 several other examples of the W VI S 3 group have been reported. 49,50,52,53 None of these compounds were prepared by oxo/sulfido substitution. A heterogeneous reaction between 14 and excess (5.5:1 mol ratio) of B 2 S 3 in acetonitrile for 4 days followed by chromatography afforded the yellow oxodisulfido com-Supporting Information Available: X-ray crystallographic data in CIF format for the 13 compounds in Tables 1-3.…”

Aggregation of PMe3-Stabilized Molybdenum Sulfides and the Catalytic Dehydrogenation of H2S

“…Nucleophilic attack of tertiary phosphine ligands at electrophilic nitrido ligands , provides a suitable precedent for the reaction Mo VI S + PMe 3 . Also potentially relevant is the recent report of phosphine adducts of d 0 -tungsten sulfides, e.g., [WS 3 (SR)(PR 3 )] - . Several reports describe the Pd 2 X 2 (dppm) 2 -catalyzed conversion of H 2 S + CH 2 (PPh 2 ) 2 → H 2 + CH 2 (PPh 2 )(P(S)Ph 2 ). − These reactions occur at room temperature with 20 turnovers over a few hours.…”