Structure of nickel bis(dimethyldithiophosphate).[1] Color code: green = Ni, yellow = S, orange = P, red = O. Selected distance and angles: P-S =198, P-O = 156, Ni-S = 222 pm and S-P-S = 103°, S-Ni-S = 88°.
Transition metal dithiophosphate complexes are coordination compounds containing dithiophosphate ligands, i.e. ligands of the formula (RO)2PS− 2. The charge-neutral complexes tend to be soluble in organic solvents, especially when R is branched. Dithiophosphates are available with a wide variety of alkoxy groups. The range of complexes is similar to those for dithiocarbamate complexes.
Oxidation of dithiophosphoric acid gives the disulfide.[4] Dithiophosphate complexes have also be prepared by oxidative addition of these disulfides:[5]
Dithiophosphates, when bidentate, are classified as L-X ligands in the Covalent bond classification method. In the usual electron counting method, they are three-electron ligands. With respect to HSAB theory, dithiophosphates are classified as soft ligands. In addition to the conventional representation, they are also described by a zwitterionic resonance structure (RO)2P+(S−)2. Phosphorus is tetrahedral.
Selected homoleptic complexes
Structure of an ligand (L) adduct of a typical zinc bis(dithiophosphate) complex. Such zinc dithiophosphate complexes are usually pentacoordinate.[6]
Homoleptic complexes have formulas M[S2P(OR)2]4, M[S2P(OR)2]3, and M[S2P(OR)2]2.
^Kastalsky, V.; McConnell, J. F. (1969). "The crystal and molecular structure of bis(dimethyldithiophosphato)nickel(II), Ni[(CH3O)2PS2]2". Acta Crystallographica Section B. 25 (5): 909–915. doi:10.1107/S0567740869003207.
^ abColdbery, David E.; Fernelius, W. Conard; Shamma, Maurice; et al. (1960). "Chromium(III) O,O ′-Diethyl Dithiophosphate". In Eugene G. Rochow (ed.). Inorganic Syntheses. Vol. 6. p. 142. doi:10.1002/9780470132371.ch44. ISBN978-0-470-13165-7. {{cite book}}: ISBN / Date incompatibility (help)
^ abDilworth, Jonathan R.; Zubieta, Jon A. (1983). "Preparation and Crystal Structure of [Mo{S2P(OMe)2}3] and an Improved Route to [MoCl3(THF)3]". Journal of the Chemical Society, Dalton Transactions (2): 397. doi:10.1039/dt9830000397.
^ abGianini, Michel; Caseri, Walter R.; Gramlich, Volker; Suter, Ulrich W. (2000). "Synthesis and Characterization of Liquid Platinum Compounds". Inorganica Chimica Acta. 299 (2): 199–208. doi:10.1016/S0020-1693(99)00499-5.
^Losada, J.; Morán, M.; Muro, Carmen (1989). "A New Synthesis and the Electrochemical Behaviour of Nickel(II) Dithiophosphate and Dithiophosphinate Complexes". Transition Metal Chemistry. 14 (2): 127–130. doi:10.1007/BF01040606.
^Ellis, Carol A.; Ng, Seik Weng; Tiekink, Edward R. T. (2007). "μ-1,4-Diazabicyclo[2.2.2]octane-κ2N: N ′-bis[bis( O , O ′-diisopropyl dithiophosphato-κ2S , S ′)zinc(II)]". Acta Crystallographica Section E. 63: m108 –m110. doi:10.1107/S1600536806052007.
^V. V. Tkachev, S. A. Shchepinov, L. O. Atovmyan (1977). "Crystal and Molecular Structure of Tetrakis(O,O"-diisopropyldithiophosphates) of Niobium(IV) and Zirconium(IV)". Zh. Strukt. Khim. (J. Struct. Chem.). 18: 1036-1041.{{cite journal}}: CS1 maint: multiple names: authors list (link)
^Furlani, C.; Tomlinson, A. A. G.; Porta, P.; Sgamellotti, A. (1970). "Preparation, Crystal Structure, and Spectroscopic Properties of Vanadium(III) Tris-(O,O-diethyl phosphorodithioate), V[PS2(OEt)2]3". Journal of the Chemical Society A: Inorganic, Physical, Theoretical: 2929. doi:10.1039/j19700002929.
^Biscarini, Paolo; Franca, Roberto; Kuroda, Reiko (1995). "Chiral Discrimination of Complexes with D3 Symmetry. Synthesis and Characterization of Tris{O,O'-bis[(+)(S)-2-methylbutyl] dithiophosphato}chromium(III) Complexes (ΛΔ){Cr[(+)(S)(S)Mebdtp]3} and Λ-(-)589-, and Δ-(+)589{Cr[(+)(S)(S)Mebdtp]3} and Crystal Packing of Racemic Tris{O,O'-diethyl dithiophosphato}chromium(III), Cr[DDTP]3". Inorganic Chemistry. 34 (18): 4618–4626. doi:10.1021/ic00122a019.
^Drew, Michael G. B.; Hopkins, William A.; Mitchell, Philip C. H.; Colclough, Terence (1986). "Preparation, Properties, and X-ray Crystal Structure of Tris(O,O′-di-isopropyl Phosphorodithioato)iron(III), [Fe{S2P(OPri)2}3]. Comparison of Structure and Bonding in Phosphorodithioato- and Dithiocarbamato-Complexes". J. Chem. Soc., Dalton Trans (2): 351–354. doi:10.1039/dt9860000351.
^Taş, Murat; Yaĝan, Mehtap; Batı, Hümeyra; Batı, Bek˙ir; Büyükgüngör, Orhan (2005). "Redetermination of Bis( O,O ′-dicyclohexyl phosphorodithioato)nickel(II)". Acta Crystallographica Section E. 61 (9): m1684 –m1685. doi:10.1107/S1600536805023895.
^ abRudzinski, Walter.; Behnke, George T.; Fernando, Quintus. (1977). "A Normal-Coordinate Analysis of Bis(O,O'-dialkyldithiophosphato)nickel(II) Complexes". Inorganic Chemistry. 16 (5): 1206–1210. doi:10.1021/ic50171a046.
^Yordanov, N.D.; Ivanova, M.; Gochev, G.; MacIcek, J. (1993). "EPR Studies on Bis(diisopropyldithiophosphato)copper(II) Magnetically Diluted in the Corresponding Palladium(II) and Platinum(II) Single Crystals and Crystal and Molecular Structure of Bis(diisopropyldithiophosphato)palladium(II) Host Lattice". Polyhedron. 12: 117–124. doi:10.1016/S0277-5387(00)87061-8.
^Yordanov, Nicola D.; Alexiev, Valentin; MacIcek, Josef; Glowiak, Tadeusz; Russell, David R. (1983). "Studies on Intermolecular Interactions of Metal Chelate Complexes. V. Copper(II) Dithiophosphate Complexes: An Example of an Inner Self-Redox Reaction". Transition Metal Chemistry. 8 (5): 257–261. doi:10.1007/BF00620863.
^Roy, Subrata; Datta, Amlan; Rehani, Sandeep (2015). "Flotation of copper sulphide from copper smelter slag using multiple collectors and their mixtures". International Journal of Mineral Processing. 143: 43–49. Bibcode:2015IJMP..143...43R. doi:10.1016/j.minpro.2015.08.008.
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