Fluorotrithiophosphate Abstraction from the Difluoropentathiodiphosphate Dianion: d⁸ and d⁶ Complexes of [η²-S₃PF]^2–

Abstract

Coordinative heterolysis of the difluoropentathiodiphosphate dianion [S 5 P 2 F 2 ] 2− results in the formal elimination of [S 2 PF] by complexes of the group 10 divalent metals nickel, palladium, and platinum. The remaining fragment of this cleavage, [S 3 PF] 2− coordinates as an η 2 -ligand. Several complexes with this novel fluorotrithiophosphate were characterized structurally and spectroscopically with X-ray diffraction (XRD), infrared (IR) spectroscopy, and 31 P and 19 F nuclear magnetic resonance (NMR). In addition to mononuclear η 2 chelate complexes, bridging complexes with η 2 -μ 2 -S 3 PF configurations result in binuclear nickel and ruthenium adducts. Facile methylation with methyl triflate of the uncoordinated sulfur atom leads to a complex with the methylthiofluorodithiophosphate ligand in a cationic complex, which hydrolyses with loss of fluoride to give complexed [S 2 P(O)SMe] 2− . Alternatively hydrolysis can also lead to a binuclear Ni 2 (dppe) 2 (S 3 PF)-(S 2 POF) complex. Divalent ruthenium π-aryl's form fluorotrithiophosphate complexes rapidly at room temperature to give bridged dimers with complete chloride substitution.

Reactions of Heterometallic Phosphinidene-Bridged MoMn and MoRe Complexes with Sulfur and Selenium: From Chalcogenophosphinidene- to Trithiophosphonate-Bridged Derivatives

“… 33 We note that in the latter complex, the trithiophosphonate ligand acts as a two-electron donor ( A in Chart 4 ). Other crystallographically characterized trithiophosphonate-bridged complexes can be classified as displaying four-electron donor ligands of type μ-κ 2 S,S′ :κ 1 S ( B ), 34 or μ-κ 2 S,S′ :κ 1 S″ ( C ) 35 and six-electron donor ligands of type μ-κ 2 S,S′ :κ 2 S,S″ ( D ). 36 The coordination mode of the six-electron donor trithiophosphonate ligand in complexes 6 is different from the above ones, and it appears to have been not identified previously, therefore adding to the set of possible coordination modes of these versatile bridging ligands ( E in Chart 4 ).…”

“…Anal. Calcd for C 28 H 34 Preparation of [MoReCp(μ-η 2 :κ 2 S,S′ -S 2 PR*)(CO) 5 ] (4). Elemental sulfur (0.016 g, 0.062 mmol of S 8 ) and compound 1a (0.050 g, 0.063 mmol) were dissolved in toluene (8 mL), and the mixture was stirred at 333 K for 2 h to give a brown solution.…”

“…Anal. Calcd for C 28 H34 MoO 5 PReS 3 : C, 39.11; H, 3.99; S, 11.19. Found: C, 39.23; H, 3.54; S, 10.93.…”