The coordination chemistry of dithiophosphonates: An emerging and versatile ligand class

doi:10.1016/j.ccr.2012.10.010

Coordination Chemistry Reviews

Volume 257, Issues 3–4, February 2013, Pages 718-731

https://doi.org/10.1016/j.ccr.2012.10.010 Get rights and content

Abstract

The phosphor-1,1,-dithiolate class of compounds is the heavier and “softer” congener of the more popular phosphonate derivatives. It contains the S₂P functionality as a common feature and several sub-categories are known which include the dithiophosphato [S₂P(OR′)₂]⁻ (R′ = typically alkyl), dithiophosphinato [S₂PR₂]⁻ (R = alkyl or aryl), and dithiophosphonato [S₂PR(OR′)]⁻ (R = typically aryl or ferrocenyl, R′ = alkyl) monoanionic ligands. The amidodithiophosphonato derivative of the type [S₂PR(NR′)]⁻, is rare. Potential dianionic monoester variants such as [H₂S₂P( double bond Q)(OR)] and [H₂S₂P(Q)R] (Q = O, S) have also been investigated. This review focuses on the dithiophosphonato [S₂PR(OR′)]⁻ ligand derivatives which have emerged as an interesting ligand choice to investigate coordination complexes. This review summarizes all reported coordination compounds utilizing dithiophosphonates with an emphasis on structure and coordination modes. It is apparent that the vast majority of compounds reported to date center around only certain metals and a large section thus remain unexplored, leaving tremendous scope and opportunity for further investigation.

Highlights

► Comprehensive review, covering all elements by group number. ► Include detailed structural analyses representing all bonding modes. ► Indicate potential future research directions using dithiophosphonates. ► Compares dithiophosphonates with related ligands.

Introduction

Dithio-organophosphorus compounds have found widespread use, not only in basic academic research, but also in diverse and important industrial areas. Applications range from anti-oxidant additives in the oil- and petroleum-industry [1] particularly zinc dithiophosphates used as a lubricant additive (anti-oxidant) for the past 60 years [2], [3] paving the way for new technology [4]; agricultural pesticide derivatives [5], [6]; and metal ore extraction reagents and flotation agents in the mining industry [7]. Within the realm of “green chemistry”, Anastas and co-workers recently suggested a structural modification in organophosphorus compounds to reduce toxicity could be achieved by replacing the present oxono analogs as acetylcholinesterase (AChE) inhibitors by the less reactive thiono analogs [8]. Aspects of the related thio- and selenophosphinic acid [9] and xanthate [10] ligands has been reviewed, but the last detailed review that covered the title ligand class as a subset of other compounds occurred in 1995 and included only 5 entries [11]. During the past two decades, however, research endeavors facilitating the formation of monoanionic dithiophosphonato ligands of the type [S₂PR(OR′)]⁻, and their systematic study as useful complexing agents for transition metal centers have grown substantially. An updated review of the topic is thus highly desirable. The present review covers all the reported coordination complexes of dithiophosphonato ligands until mid-2012 and focuses on those compounds that contain reported X-ray crystal structures.

Section snippets

Dithiophosphonates as a class of phosphor-1,1-dithiolates

The chemistry of the symmetrical dithiophosphato, [S₂P(OR)₂]⁻ and dithiophosphinato, [S₂PR₂]⁻ ligands has been well developed [12], [13], [14], [15], [16], [17], [18], [19], with reviews specifically aimed at antimony, arsenic and bismuth as well [20], [21], [22]. The dithiophosphonato ligand, [S₂PR(OR′)]⁻, however, is far less developed but of interest mainly for the following reasons: (i) it can still be considered comparatively rare in the chemical literature and indeed for the majority of

Conclusions and outlook

The chemistry of the dithiophosphonates and their metal complexes is by no means a mature field of research and many more exciting discoveries with the title ligands can be expected. The scope shown here among all metals makes it clear where more discoveries can be made. But even in areas where productivity has been shown, more can be done, for example, the area of gold(III) dithiophosphonate complexes seems to be completely unexplored. Modification of the ligand toward formation of water

Acknowledgement

WEvZ thanks John P. Fackler, Jr. in whose labs interest in metal dithiophosphonate chemistry was initiated, and all the students in my group who have contributed to this research since then.

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A series of isomorphic cobalt(II), nickel(II) and zinc(II) complexes of mixed dithiophosphonate, 2,2-bipyridine and 1,10-phenanthroline ligands: Synthesis, structure, and theoretical calculations
2023, Inorganica Chimica Acta
Transition-metal complexes of dithiophosphonate ligands have attracted recent interest due to their involvement in several established and newly emerging applications. Herein, we report on the synthesis of six new complexes of Co(II), Ni(II), and Zn(II) and mixed dichalcogen (dithiophosphonate) and dipnictogen (2,2-bipyridine, and 1,10-phenanthroline) ligands: [Co{(S₂P(4-C₆H₄OMe)(OCH(CH₂CH₃)₂}₂(C₁₀H₈N₂)] 1, [Co{(S₂P(4-C₆H₄OMe)(OCH₂CH₂CH₂CH₃)}₂(C₁₀H₈N₂)] 2, [Ni{S₂P(4-C₆H₄OMe)(OCH₃)}₂(C₁₂H₈N₂)] 3, [Ni{(S₂P(4-C₆H₄OMe)(OCH(CH₂CH₃)₂)}₂(C₁₂H₈N₂)] 4, [Zn{(S₂P(4-C₆H₄OMe)(OCH₃)}₂ (C₁₂H₈N₂)] 5 and [Zn{(S₂P(4-C₆H₄OMe)(OCH₂CH₃)}₂(C₁₂H₈N₂)] 6. The complexes were characterized by solution ¹H and ³¹P NMR spectroscopy, electrospray ionization mass spectrometry, elemental analysis, and FTIR. The crystal structures of 1, 3, 5, and 6 were established by single-crystal X-ray diffraction analysis. The four complexes are isomorphic and crystallize in the triclinic system, space group P-1, with Z = 2. Density functional theory (DFT) calculations of the electronic and structural properties of the complexes were carried out to estimate different quantum chemical properties. Crystallographic analysis showed that the Co(II) and Ni(II) metal centers in 1 and 3, respectively, adopted a distorted octahedral geometry, coordinating through the S (dithiophosphonate) and N (dipnictogen) donor atoms, while the Zn(II) center in 5 and 6 both adopted tetrahedral geometries. The obtained computational-based chemical parameters proved to be significant in evaluating the plausible reactivity and stability patterns of these complexes.
2,4-Bis(2,4-dimethoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide and its derivatives: Syntheses, structural characterizations, anticancer activities, and theoretical studies on some dithiophosphonato Ni(II) complex
2023, Journal of Molecular Structure
Citation Excerpt :
For example, Zn(II), Cd(II) and Hg(II) are prone to form dimeric complexes with tetrahedral geometries [14,15]. Group 10 cations, Ni(II), Pd(II) and Pt(II), on the other hand, form monomeric complexes with square planar coordination geometry [15–18]. Dithiophosphonato- and dithiophosphinato complexes of Ni(II), namely [Ni(DTPOA)2] and [Ni(DTPA)2], are prepared by the direct reaction of 1,3,2,4-dithiadiphosphetane 2,4-disulfides (Lawesson reagent, (LR), for example), with an monofunctional alcohol, ROH [19] or with a Grignard reagent, R-MgX [20], respectively (Scheme 1).
New 2,4-bis(2,4-dimethoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide, (SAV-A2), was synthesized from the reaction P₄S₁₀ and 1,3-dimethoxybenzene. SAV-A2 was reacted with alcohols to form dithiophosphonic acid monoesters (HLn, HS₂P((2,4-CH₃O)₂C₆H₃)(ORn); n=1–3, R1=2‑butyl‑; R2=n-pentyl-; R3=4‑tert‑but-benzyl-). The acids were converted to the ammonium salts ([NH₄Ln]) to serve as the source of the ligands (Ln), to obtain Ni(II) complexes, ([Ni(Ln)₂]). [Ni(L2)₂] crystal structure was elucidated by single-crystal X-ray diffraction analysis. In addition, Density Functional Theory (DFT) calculations of [Ni(L2)₂] was performed. The molecular docking studies of the complex with liver cancer protein, PDB ID: 3WZE and colon cancer antigen proteins, ID 2HQ6 were done compare with experimental and theoretical results. All compounds were tested on liver- and colon cancer cell lines. Among the complexes tested, [Ni(L3)₂] showed an activity closer to that of cisplatin against the colon cancer cell line. The other compounds were found to be have less active.
Is the phosphorous atom a stereogenic center? Crystallographic findings in five new dithiophosphonate compounds supported with non covalent interaction index (NCI), theoretical approach and spectroscopic analysis
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The self-assembly of the dithiophosphonate tectons synthesized in this work generated novel supramolecular synthonsvia NH···S, NH···O, CH···S, CH···O, CH···π, and lp···π interactions. The reaction of the salts with chloro dithiastibocanes X(CH₂CH₂S)₂SbCl (X = O, S) led to the formation of coordination compounds in which the crystal structures showed two new supramolecular synthons stabilized by CH···π and lp···π interactions. The theoretical study of the electronic density of the crystal and their synthons in the solid-state used the robust NCI index to confirm the nature of the interactions found. This study confirmed the connection between molecular and supramolecular chirality in the crystalline state. Three significant features unequivocally support the findings: the role of intramolecular interactions, the electronic density differences among diastereomers, and the nature of trans-annular bonds. The characterization of the salts: ammonium-menthoxy (4-methoxyphenyl) dithiophosphonate (1), triethylammonium-menthoxy (4-methoxyphenyl)-dithiophosphonate (2), triethylammonium-biphenyl-4‑methoxy (4-methoxyphenyl) dithiophosphonate (3), and the coordination compounds O(CH₂CH₂S)₂Sb[S₂P(biphenyl-4‑methoxy)(4-MeOC₆H₄)] (4) and S(CH₂CH₂S)₂Sb[S₂P(biphenyl-4‑methoxy)(4-MeOC₆H₄)] (5) was carried out by elemental analyses, IR, NMR (¹H, ¹³C, ³¹P), and single-crystal X-ray diffraction analysis.
Synthesis, characterization, and biological evaluation of eight new organotin(IV) complexes derived from (1R, 2S) ephedrinedithiocarbamate ligand
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The synthesis of eight new organotin derivatives containing ephedrine-substituted dithiocarbamate ligands [R₃Sn(ephedtc)] 2–5. 2: R = Me; 3: R = Bu; 4: R = Cy; 5: R = Ph and [R₂Sn(ephdtc)₂] 6–9. 6: R = Me; 7: R = Bu; 8: R = t-Bu; 9: R = Ph is reported. The complexes were obtained from sodium ephedrinedithiocarbamate [Na(ephedtc)] 1 and the corresponding tri-organotin(IV) chlorides, R₃SnCl 2–5 or di-organotin(IV) dichlorides, R₂SnCl₂ 6–9. They were characterized by elemental analysis, IR, and NMR spectroscopy (¹H, ¹³C, and ¹¹⁹Sn). The infrared spectra (solid-state) suggest that the Sn(IV) is coordinated to the ligand ephedtc, through the two sulfur atoms in an anisobidentate coordination mode. In solution, the ¹¹⁹Sn NMR indicates the coordination numbers: tetracoordinated for 2–4, pentacoordinate for 5, and hexacoordinated for 6–9. The single-crystal X-ray diffraction analysis of 4 reveals an anisobidentate coordination mode with a trigonal bipyramid distorted geometry around the Sn(IV). All compounds except 2, show inhibition in at least one bacterial strain, and 7 and 9 have the best antibacterial activity, mainly in the clinically isolated strains.
Ferrocene decorated homoleptic silver(I) clusters: Synthesis, structure, and their electrochemical behaviour
2021, Journal of Organometallic Chemistry
Citation Excerpt :
Dithiophosphonates ligands having aryl (R’ = 4-C6H4OR) group framed various heteroleptic copper(I) complexes ranging from single metal centre [Cu{S2P(4-C6H4OR)(OMe)}{PPh3}2] (R = Me, Et) [13], dinuclear [Cu2(μ2ArS2POPS2Ar)(PPh3)4] (Ar = 4-C6H4OMe) [14], distorted tetrahedral [Cu4{Ar(μ2-S)2POP-(μ2-S)2Ar}2(dppa)2] (dppa = Ph2PNHPPh2) [14], luminescent [Cu4{(S2P(1,4-C6H4OMe)(OR’)}4] (R’ = OCH(CH3)2; CH2C6H5) [15] and a larger [Cu14(μ6ArP(O)S2)6(μ3-ArP(O)(OAc)S)2(PPh3)6] [16]. In case of Au(I), there were characterized heteroleptic mononuclear [Au{S2P(OMe)(p-C6H4OEt}{PPh3}] [13], [Au{S2P(4-C6H4OMe)(OC5H9)}{PPh3}2] [17], and few of dinuclear gold(I) of the type {[AuS2PR`(OR)]2} [18], with varying of R group and interesting structural features were well documented.To the best of our knowledge, the mononuclear silver(I) dithiophosphonate complex were not known, like Cu and Au. [11,12]. However, a few number of heteroleptic Ag(I) arylated dithiophosphonate complexes were also characterized having nuclearity from dinuclear [Ag{S2P(OMe)(4-C6H4OEt}{PPh2}]2 [13], dimer of [Ag2{ArP(O)S2}(dppm)2] in rectangle plane [19], and high nuclearity [Ag20(ArP(OEt)S2)6(ArPOS2)6(Ph3P)8(OAc)2] [20], [Ag28(μ6-S)2{ArP(O)S2}12-(PPh3)12] [19].
Silver(I) ferrocenyl dithiophosphonato [Ag{S₂P(OⁱPr)Fc}]_n I, [Fc = Fe(η⁵-C₅H₄)(η⁵-C₅H₄)] 1D polymer was yielded via a ligand exchange reaction between silver nanocluster [Ag₂₁(S₂P(OⁱPr₂)₁₂)]PF₆ and monoanionic [S₂P(OⁱPr)Fc]^¯ ligand. As per molecular stoichiometry of 1, a direct reaction between [Ag(CH₃CN)₄]PF₆ and [S₂P(OⁱPr)Fc]⁻ was performed in methanol solvent and surprisingly, generate a tetrahedral Ag₄{S₂P(OⁱPr)Fc}₄ 2 cluster instead of 1. Both (1 and 2) clusters are the novel example of homoleptic Ag(I) complexes supported by ferrocenyl dithiophosphonates. Molecular structure of these clusters was unequivocally established by single crystal X-ray crystallographic analyses and supported by the ESI-MS, and ¹H and ³¹P NMR spectroscopy. Structural elucidations reveal that compound 1 has subsequently Ag₂S₂ square plane and Ag₂S₄P₂ twisted boat units to build a long chain 1D polymer. The cluster 2 exhibits with a tetrahedral Ag(I) core framed by four [S₂P(OⁱPr)Fc]⁻ ligands. interstingly, the [S₂P(OⁱPr)Fc]⁻ ligand display a trimetallic triconnective (η³; µ_1, µ₂) bonding pattern in both molecules. The electrochemical behaviours of both compounds (1 and 2) were studied by using cyclic voltammetry, which shows a single wave for all the peripheral ferrocenes and implies negligible electrostatic factor between all ferrocene moieties.
Dinuclear metal complexes of a new hybrid phosphine-phosphonodithioate ligand
2021, Journal of Organometallic Chemistry
Reaction of Ph₂PCH₂OH and {RP(S)(μ-S)}₂ (R = p-C₆H₄OMe, Lawesson's reagent), in toluene, gave the new hybrid P^III/P^V ligand Ph₂PCH₂OP(S)(R)SH 1 in high yield. Unfortunately, attempts to crystallise 1 gave, instead, suitable X-ray quality crystals of the Zwitterion Ph₂P⁺(CH₂OH)CH₂OP(S)(R)S⁻ 1′, presumably arising from the presence of some residual formaldehyde. Three homodinuclear complexes [Ru₂(η⁶-p-CH₃C₆H₄ⁱPr)₂{μ-Ph₂PCH₂OP(S)(R)S}Cl₃] (2) and [M₂(η⁵-C₅(CH₃)₅)₂{μ-Ph₂PCH₂OP(S)(R)S}Cl₃] [M = Rh, 3; M = Ir, 4 (R = p-C₆H₄OCH₃)] were obtained upon reaction of a 1:1 molar ratio of 1 and either [(η⁶-p-CH₃C₆H₄ⁱPr)RuCl(μ-Cl)]₂ or [M(μ-Cl)(Cl)(η⁵-C₅(CH₃)₅)₂]₂ (M = Rh and Ir), respectively. The mononuclear Ir^III complex Ir(η⁵-C₅(CH₃)₅)(Ph₂PCH₂OH)Cl₂ 5 was prepared for comparative spectroscopic and crystallographic purposes with 4. All compounds were characterised by a combination of multinuclear NMR and FT−IR spectroscopy and elemental analysis. In addition, the first example of a phosphine-dithiophosphonate ligand 1′ along with two homodinuclear complexes 2·CHCl₃ and 4 were determined by single crystal X-ray diffraction. Compound 5 displays an intramolecular O(1)−H(1)···Cl(2) hydrogen bond to a terminal Ir^III bound chloride ligand.

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ReviewThe coordination chemistry of dithiophosphonates: An emerging and versatile ligand class

Abstract

Highlights

Introduction

Section snippets

Dithiophosphonates as a class of phosphor-1,1-dithiolates

Conclusions and outlook

Acknowledgement

Tribol. Int.

Tribol. Int.

Toxicol. Appl. Pharmacol.

Hydrometallurgy

Polyhedron

J. Organomet. Chem.

Coord. Chem. Rev.

Coord. Chem. Rev.

Coord. Chem. Rev.

Sov. J. Coord. Chem. (Engl.)

Dalton Trans.

Bull. Soc. Chim. Belg.

Tetrahedron

Russ. J. Gen. Chem.

New J. Chem.

Russ. J. Gen. Chem.

Polyhedron

J. Organomet. Chem.

Lubricants and Related Products

Lubr. Sci.

A Comprehensive Guide to Hazardous Properties of Chemical Substances

Chem. Rev.

Angew. Chem. Int. Ed. Engl.

Rev. Inorg. Chem.

Polyhedron

Fortschr. Chem. Forsch.

Rev. Inorg. Chem.

Acc. Chem. Res.

Main Group Met. Chem.

CrystEngComm

Coord. Chem. Rev.

Nomenclature of Inorganic Chemistry (Red Book II). Recommendations 2000

Nomenclature of Inorganic Chemistry – IUPAC Recommendations 2005

A Guide to IUPAC Nomenclature of Organic Compounds. Recommendations 1993. A Guide to the Blue Book

J. Chem. Soc. Dalton Trans.

Coord. Chem. Rev.

Inorg. Chim. Acta

Sov. J. Coord. Chem. (Engl.)

Miscellanea Berolinensia

Justus Liebigs Ann. Chem.

Chem. Ber.

Helv. Chim. Acta

Proc. Kon. Ned. Akad. Wetensch.

Proc. R. Soc. Ser. A (Lond.)

Natl. Pet. News

Chem. Abs.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Justus Liebigs Ann. Chem.

Chim. Ind. (Milan)

Review
The coordination chemistry of dithiophosphonates: An emerging and versatile ligand class