A difluorodithiophosphate is an anion or chemical compound with phosphorus connected to two sulfur atoms and two fluorine atoms. It has a single negative charge. The formula is [S2PF2]−.
Related compounds are the fluorodithiophosphates, difluoropentathiodiphosphates ([S5P2F2]2–), fluorotrithiophosphates ([S3PF]2–) and the difluorothiophosphates (F2P(O)S−). Fluorine can also be substituted by trifluoromethyl, phenyl, methyl or ethoxy groups.
Formation Salts containing difluorodithiophosphate can be made by reacting difluorodithiophosphoric acid (HS2PF2) with electropositive metals. Less electropositive metals salts may be produced by a reaction of the acid with the metal oxide or chloride.
Other ways it can be produced are in a reaction of dimethylamine with thiophosphoryl fluoride (SPF3).
Properties Thermal decomposition of difluorodithiopgosphate salts yields thiophosphoryl fluoride and phosphorus trifluoride.
Some compounds with two or three difluorodithiophospate groups are monomeric, dissolving in benzene, and being quite volatile, meaning they can be sublimed. Other solvents include toluene, heptane and 1,2-dichloroethane.
List formulanamecrystalspace groupunit cellvolumedensitycommentrefH[S2PF2]difluorodithiophosphoric acidliquidboil 72°; colourless[(C3H7)4N][S2PF2]tetrapropylammonium difluorodithiophosphateorthorhombicPbcaa=14.9466 b=14.6702 c=16.8033 Z=83684.51.151(CH3)3SiSP(S)F2trimethylsilyl difluorodithiophosphate−79.7°[(C6H5)4PS2PF2KS2PF2Cl3Ti[S2PF2]V[S2PF2]3tris(difluorodithio-phosphinato)vanadium (111)deep red-brown; mp ~46.5OV[S2PF2]2blackCr[S2PF2]3deep purple; volatile; mp 52°Mn[S2PF2]2pinkMn(CO)3P(C6H5)3S2PF2yellow; melt ~119°Mn(CO)3P(C6H5)2C2H4P(C6H5)2SP(S)F2yellow-orangeFe[S2PF2]2tan mp=~80 °Cπ-C5H5Fe(CO)2S2PF2pi-cyclopentadienyl iron dicarbonyl difluorodithiophosphateyellow-brown; decompose 95 °C(ON)2Fe[S2PF2]rusty-red; mp 69-70°Co[S2PF2]2green; mp=44° volatile(ON)2Co[S2PF2]brownCo[S2PF2]3brown mp 34° volatileNi[S2PF2]2dark green mp ~43° volatileCu[S2PF2]off-white dec >400°(Ph3P)2Cu[S2PF2]white dec 200°Zn[S2PF2]2mp ~157°Cl3Nb[S2PF2]ochre colouredCl3Nb[S2PF2]2trichlorobis(difluorodithio-phosphinato)niobium(Y)orangeMo[S2PF2]3red; mp 62°; volatileOMo[S2PF2]2greenπ-C5H5Mo(CO)3SP(S)F2red-orange; decompose ~ 102 °Cπ-C5H5Mo(CO)2S2PF2purple; melt 39°Pd[S2PF2]2orange mp 56.5° volatile(Ph3P)Pd[S2PF2]2orange mp 141°(Ph3P)2Pd[S2PF2]2yellow dec 160°(p-Me-Ph3P)Pd[S2PF2]2orange 189°(p-Me-Ph3P)2Pd[S2PF2]2yellow dec 172°(Ph3As)Pd[S2PF2]2orange mp 122°(n-C3H7)4NPd[S2PF2]3yellow dec 160°Rh[S2PF2]3volatileRh(CO)2[S2PF2]orange-red; mp 48°Rh(CO)(P(C6H5)3)[S2PF2]yellowRh(CO)(As(C6H5)3)[S2PF2]brownish-redRh(CO)(Sb(C6H5)3)[S2PF2]brownish-redRu[S2PF2]3reddish-orange mp 54°triclinicP-1a=11.127 b=12.345 !!! c=13.689 α=88.239° β=81.183° γ=76.965° Z=21810.21.489monoclinicP21/ca=17.325 b=10.1385 c=20.967 β=104.443° Z=435661.531monoclinicC2/ca=39.987 b=9.9967 c=21.910 β=116.810° Z=87731.01.601Ru(CO)(η1-S2PF2)(η2-S2PF2)(PPh3)2cistriclinicP-1a=12.271 b=13.058 c=15.012 α=80.397° β=82.335° γ=63.243°2113.11.595Ru(CO)(η1-S2PF2)(η2-S2PF2)(PPh3)2transmonoclinicP21/na=13.279 b=20.031 c=15.762 β=91.664° Z=44191.01.589Ag[S2PF2]white mp ~150°Cd[S2PF2]2dec 173°(CH3)2ClSnSP(S)F2dimethylstannyl chloride difluorodithiophosphatemelt 6.4°CsS2PF2dec 298°Cl3Ta[S2PF2]2yellowOWCl[S2PF2]2olive brownCl2W[S2PF2]3brownπ-C5H5W(CO)3SP(S)F2rust coloured; dec 75°Pt[S2PF2]2yellow mp ~53.5° volatile(Ph3P)Au[S2PF2]mp 98°Hg[S2PF2]2dec 163°Ph=phenyl; Me=methylg/ccmp = melting point °C dec = decomposes
References