Chemistry:Transition metal dithiophosphate complex

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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.

Preparation

Dithiophosphate ligands are prepared by alcoholysis of phosphorus pentasulfide:[2]

P
4S
10 + 8 C
2H
5OH → 4 (C
2H
5O)
2PS
2H + 2 H
2S

Dialkoxydithiophoric acids react with many metal oxides, chlorides, and acetates:[2]

3 (C
2H
5O)
2PS
2H + CrCl
3(H
2O)
6 → Cr[S
2P(OC
2H
5)
2]
3 + 3 HCl + 6 H
2O

Alternatively, salts, such as ammonium diethyldithiophosphate, can be used to prepare complexes by salt metathesis reactions:[3]

2 NH
4[S
2P(OC
2H
5)
2] + NiCl
2 · (H
2O)
6 → Ni(S
2P(OC
2H
5)
2) + 6 H
2O + 2 NH
4Cl
3 NH
4[S
2P(OCH
3)
2] + MoCl
3(thf)
3 → Mo[S
2P(OCH
3)
2]
3 + 3 NH
4Cl + 3 thf (thf = tetrahydrofuran)

Oxidation of dithiophosphoric acid gives the disulfide.[4] Dithiophosphate complexes have also be prepared by oxidative addition of these disulfides:[5]

[S
2P(OC
2H
5)
2]
2 + Ni(P(OC
6H
5)
3)
4 → Ni(S
2P(OC
2H
5)
2)
2 + 4 P(OC
6H
5)
3

Ligand properties

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[S
2P(OR)
2]
4, M[S
2P(OR)
2]
3, and M[S2P(OR)2]2.

  • Zr[S
    2    P(OC
    3    H
    7    )
    2    ]
    4    [7]
  • V[S
    2    P(OC
    2    H
    5    )
    2    ]    3, red-brown,[8]
  • Cr[S
    2    P(OC
    2    H
    5    )
    2    ]
    3    , violet[9]
  • Mo[S
    2    P(OCH
    3    )
    2    ]
    3    , red[3]
  • Fe[S
    2    P(OC
    3    H
    7    )
    2    ]
    3    [10]
  • Ru[S
    2    P(OC
    2    H
    5    )
    2    ]
    3    [11] pink, paramagnetic
  • Ir[S
    2    P(OC
    3    H
    7    )
    2    ]
    3    [12]
  • Ni[S
    2    P(OC
    6    H
    11    )
    2    ]
    2    [13] violet[14]
  • Pd[S
    2    P(OC
    2    H
    5    )
    2    ]
    2    [15]
  • Pt[S
    2    P(OC
    2    H
    5    )
    2    ]
    2    [4] yellow, diamagnetic[14]
  • Cu[S
    2    P(OC
    6    H
    4    CH
    3    )
    2    ]
    2    [16]
  • poly-Zn[S
    2    P(OC
    2    H
    5    )
    2    ]
    2    [17]

These complexes are almost always solids at room temperature.

Applications

Zinc dialkyldithiophosphates are components of oil additives.[18][19] Dithiophosphate complexes are also implicated as intermediates in froth flotation, e.g. for the purification of copper from slag.[20]

References

  1. ↑ 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. 
  2. ↑ 2.0 2.1 Coldbery, David E. et al. (1960). "Chromium(III) O,O ′-Diethyl Dithiophosphate". in Eugene G. Rochow. Inorganic Syntheses. 6. p. 142. doi:10.1002/9780470132371.ch44. ISBN 978-0-470-13165-7. 
  3. ↑ 3.0 3.1 Dilworth, 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. 
  4. ↑ 4.0 4.1 Gianini, 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. 
  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. 
  6. ↑ Ellis, Carol A.; Ng, Seik Weng; Tiekink, Edward R. T. (2007). "μ-1,4-Diazabicyclo[2.2.2]octane-κ2 N: N ′-bis[bis( O , O ′-diisopropyl dithiophosphato-κ2 S , S ′)zinc(II)]". Acta Crystallographica Section E 63: m108–m110. doi:10.1107/S1600536806052007. 
  7. ↑ 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. 
  8. ↑ 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. 
  9. ↑ 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. 
  10. ↑ 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. 
  11. ↑ Jain, Prateek U.; Munshi, Pradip; Walawalkar, Mrinalini G.; Rath, Sankar Prasad; Rajak, Kajal Krishna; Lahiri, Goutam Kumar (2000). "Ruthenium Dithiophosphates: Synthesis, X-Ray Crystal Structure, Spectroscopic and Electrochemical Properties". Polyhedron 19 (7): 801–808. doi:10.1016/S0277-5387(00)00316-8. 
  12. ↑ Marsh, R. E. (1995). "Some Thoughts on Choosing the Correct Space Group". Acta Crystallographica Section B 51 (6): 897–907. doi:10.1107/S0108768195008901. Bibcode: 1995AcCrB..51..897M. https://resolver.caltech.edu/CaltechAUTHORS:20170124-095650147. 
  13. ↑ 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. 
  14. ↑ 14.0 14.1 Rudzinski, 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. 
  15. ↑ 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. 
  16. ↑ 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. 
  17. ↑ T. Ito; T. Igarashi; H. Hagihara (1969). "The Crystal Structure of Metal Diethyldithiophosphates. I. Zinc Diethyldithiophosphate". Acta Crystallogr. B 25 (11): 2303–2309. doi:10.1107/S0567740869005619. Bibcode: 1969AcCrB..25.2303I. http://journals.iucr.org/b/issues/1969/11/00/a06973/a06973.pdf. 
  18. ↑ "Zinc dialkyl dithiophosphates". https://www.acs.org/molecule-of-the-week/archive/z/zinc-dialkyl-dithiophosphates.html. 
  19. ↑ Spikes, H. (2004-10-01). "The History and Mechanisms of ZDDP" (in en). Tribology Letters 17 (3): 469–489. doi:10.1023/B:TRIL.0000044495.26882.b5. ISSN 1023-8883. 
  20. ↑ 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. doi:10.1016/j.minpro.2015.08.008. Bibcode: 2015IJMP..143...43R. 



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