ReviewThe coordination chemistry of dithiophosphonates: An emerging and versatile ligand class
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.
References (190)
- et al.
Tribol. Int.
(2001) - et al.
Tribol. Int.
(2005) Toxicol. Appl. Pharmacol.
(1969)- et al.
Hydrometallurgy
(1993) - et al.
Polyhedron
(1995) J. Organomet. Chem.
(2001)- et al.
Coord. Chem. Rev.
(1984) - et al.
Coord. Chem. Rev.
(1996) - et al.
Coord. Chem. Rev.
(2003) - et al.
Sov. J. Coord. Chem. (Engl.)
(1978)
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)
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Ferrocene decorated homoleptic silver(I) clusters: Synthesis, structure, and their electrochemical behaviour
2021, Journal of Organometallic ChemistryCitation 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].
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