Accepted Manuscript

Title: The coordination chemistry of dithiophosphonates: an

emerging and versatile ligand class

Authors: Werner E. van Zyl, J. Derek Woollins

PII: S0010-8545(12)00259-7
DOI: doi:10.1016/j.ccr.2012.10.010
Reference: CCR 111649

To appear in: Coordination Chemistry Reviews

Received date: 26-7-2012

Revised date: 12-10-2012
Accepted date: 18-10-2012

Please cite this article as: W.E. van Zyl, J.D. Woollins, The coordination chemistry of
dithiophosphonates: an emerging and versatile ligand class, Coordination Chemistry
Reviews (2010), doi:10.1016/j.ccr.2012.10.010

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Edited Oct 18 

The coordination chemistry of dithiophosphonates: an emerging

and versatile ligand class

Werner E. van Zyla,* and J. Derek Woollinsb

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a
School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private Bag

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X54001, Durban, 4000, South Africa
Email: vanzylw@ukzn.ac.za

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b
EaStCHEM School of Chemistry, University of St Andrews, Fife KY16 9ST, United Kingdom

Abbreviations
an
ac-py = acetylpyridine; Ar = 4-anisyl (4-C6H4OMe); tBu = tertiary butyl; COD = 1,5-
M
cyclooctadiene; Cp = cyclopentadienyl; Cp* = pentamethylcyclopentadienyl; DCM =
dichloromethane; DME = dimethylformamide; dppa = bis(diphenylphosphino)amine; dppm =
bis(diphenylphosphino)methane; dppe = bis(diphenylphosphino)ethane; dppb =
bis(diphenylphosphino)butane; en = ethylenediamine; Et = ethyl; Fc = ferrocenyl; FcLR =
d

ferrocenyl Lawesson’s Reagent; LR = Lawesson’s Reagent; iPr = iso-propyl; Me = methyl; OAc

= acetate; Ph = phenyl; py = pyridine; solv = solvent; THF = tetrahydrofuran; tptz = 2,4,6-tris(2-
e

pyridyl)-1,3,5-triazine
pt
ce
Ac

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ABSTRACT an
The phosphor-1,1,-dithiolate class of compounds is the heavier and “softer” congener of the
M
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’ =
d

typically alkyl), dithiophosphinato [S2PR2]¯ (R = alkyl or aryl), and dithiophosphonato

e

[S2PR(OR’)]¯, (R = typically aryl or ferrocenyl, R’ = alkyl) monoanionic ligands. The

amidodithiophosphonato derivative of the type [S2PR(NR’)]¯, is rare. Potential dianionic
pt

monoester variants such as [H2S2P(=Q)(OR)] and [H2S2P(=Q)R] (Q = O, S) have also been

investigated. This review focuses on the dithiophosphonato [S2PR(OR’)]¯ ligand derivatives
ce

which have emerged as an interesting ligand choice to investigate coordination complexes. This
review summarizes all reported coordination compounds utilizing dithiophosphonates with an
Ac

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. (191 References).

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Keywords: Dithiophosphonato; Phosphonodithioate; Synthesis; Structures; Coordination modes;

Metal complexes; Anhydride route

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1. Introduction
an
M
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
d

additives in the oil- and petroleum industry [1] particularly zinc dithiophosphates used as a
e

lubricant additive (anti-oxidant) for the past 60 years [2,3] paving the way for new technology
pt

[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
ce

recently suggested a structural modification in organophosphorus compounds to reduce toxicity

could be achieved by replacing the present oxono analogues as acetylcholinesterase (AChE)
inhibitors by the less reactive thiono analogues [8]. Aspects of the related thio- and
Ac

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 1996 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

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all the reported coordination complexes of dithiophosphonato ligands until mid-2012 and focuses
on those compounds that contain reported X-ray crystal structures.

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

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The chemistry of the symmetrical dithiophosphato, [S2P(OR)2]¯ and dithiophosphinato, [S2PR2]¯
ligands has been well developed [12-19], with reviews specifically aimed at antimony, arsenic

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and bismuth as well [20-22]. The dithiophosphonato ligand, [S2PR(OR’)]¯, however, is far less
developed but of interest mainly for the following reasons: i) it can still be considered

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comparatively rare in the chemical literature and indeed for the majority of main- and transition-
metals scarce to non-existent; ii) from the reaction between common dimeric precursors (usually
an
Lawesson’s Reagent), and any compound that contains a primary or secondary alcohol
functionality, a tremendous number of new and varied derivatives can be obtained in a facile
manner; iii) the synthetic methodology allows for control in the design of the ligand (with
M
respect to solubility and materials properties, and steric effects, etc.) to perform reactions and
yield new products in both organic and also aqueous phases; iv) the asymmetric nature of the
d

ligand allows for complex isomers to be formed which often impose a unique challenge, a
feature not possible for the aforementioned symmetrical ligands; and v) solution and solid state
e

31
P NMR spectroscopy is a valuable tool to obtain mechanistic and structural information.
pt
ce

2.1 Nomenclature
Ac

The phosphor-1,1 dithiolate class of compounds is varied and include, amongst others, the
dithiophosphates A, dithiophosphinates B, dithiophosphonates C, and related
amidodithiophosphonates D, shown with delocalization of electron density across the S-P-S
bonds in Chart 1. The dithiophosphonato ligand, C, may be described as a hybrid of A and B and
represents the major ligand type that is the subject of this review.

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Chart 1. Different types of phosphor-1,1,-dithiolates. *Designates Chemical Abstracts

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Services (CAS) and “Preferred IUPAC Names” (PIN) nomenclature.

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For several decades the nomenclature for metal dithiophosphonates has been inconsistently
applied. In this regard phosphonic acid, HPO(OH)2, is the parent acid of the phosphonate anion,
an
[HPO3]2- from which all title ligands in this review are derived. The IUPAC systematic name for
HPO(OH)2 is hydridodihydroxydooxidophosphorus whilst its common name is phosphonic acid.
Systematic names are thus seldom used, instead so-called “preferred IUPAC names” (PIN) are
M
used. A PIN is a name that is preferred among two or more IUPAC names, but “the existence of
preferred IUPAC names does not prevent the use of other names…” [23]. This implies that as
d

long as there is no ambiguity, the reader being addressed must be considered in the type of
nomenclature that is used since no single correct form currently exists. Furthermore, the 1990,
e

2001, and most recent 2005 IUPAC recommendations of Nomenclature of Inorganic Chemistry
pt

(Red Book) gives no guidance as to the naming of a phosphonate derivative containing a P-C
bond and thio infix [24]. More useful information is found in Nomenclature of Organic
ce

Chemistry (Blue Book), published in 1979, with a 1993 update and the recent 2004 draft
Recommendations [25]. According to these recommendations, the acid R(OR’)P(S)(SH) is
Ac

named a phosphonodithoic acid, and anions are named by changing the ‘ic acid’ ending to ‘ate’,
i.e. phosphonodithioate, and neutral salts and esters are both named using the name of the anion
derived from the name of the acid. This review will use dithiophosphonato when describing a
ligand as a formal coordination entity, and dithiophosphonate when referring to an anion, usually
in the context of the deprotonated acid.

2.2 Resonance
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The dithiophosphonato ligand can be described by the contributing resonance structures

shown in Chart 2.

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Chart 2. Contributing resonance structures for dithiophosphonato ligands.

an
Depending on the metal type, oxidation state and coordination geometry, resonance structures E,
F or G typically predominates. Resonance structures E and F have been observed for complexes
where the ligand binds in a μ1-fashion (anisobidentate) with a dangling sulfur atom, for example,
M
in many Pb(II), Hg(II), and Zn(II) complexes. Resonance structure G predominates in many
dinuclear Au(I) complexes, as well as in the common Ni(II) isobidentate chelating mononuclear
d

complexes. Evidence of G is usually shown by the two equal P-S bond lengths in the solid state.
e

Structure H is unknown for metal dithiophosphonates but included here for completeness as the
result of a study by Drew and co-workers where a comparison in donor strength between
pt

dithiophosphates and dithiocarbamates were made [26]. A difference between these two dithio-
ce

species was rationalized [27] by proposing the dithiocarbamates, [S2C-NR2]¯, have two negative
charges on the sulfur atoms, and a positive charge on the nitrogen, (related to G), giving
enhanced electron density on the sulfur atoms while in resonance H “the electron density is
Ac

diminished by back-donation from the sulfur to the 3d orbitals of the phosphorus”. There is thus
less covalency in the M-S bond in the dithiophosphates than in the dithiocarbamates, a
conclusion in accordance with X-ray photoelectron and UV photoelectron spectroscopic
measurements, as well as quantum mechanical calculations [28-30]. The resonance structures
play a major part in the description of bonding modes.

2.3 Coordination modes

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The phosphor-1,1,-dithiolato set of ligands can coordinate to virtually all main group and
transition metals, giving rise to a wide variety of coordination patterns. The major coordination
patterns are summarized in Chart 3 categorized from mono- to tetranuclear metal centers and
from mono- to tetraconnective. Connectivity here refers to the number of connections between

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donor atoms of the ligands and the coordinated metal atom [14]. Such connections do not
discriminate between covalent, dative-coordinate or weak van der Waals interactions. A

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complete description of the coordination involved can thus only occur in conjunction with
detailed X-ray analysis. Table 1 summarizes the main structural data indicating the diversity in

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bonding modes and variation of key bond lengths and angles.

an
M
e d
pt
ce
Ac

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an
M
e d
pt
ce
Ac

Chart 3. A summary of the major known (blocked), and potential coordination bonding modes
of dithiophosphonato ligands.

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Table 1. Summary of structural data for metal dithiophosphonates.

an
_____________________________________________________________________________________________________________________

Complex P-S (Å) M-S (Å) S-P-S (°) S-M-S (°) Bond type Ref.

M
or M-P-S* (°)

_________________________________________________________________________________________________________________________________

ed
K2[C10H6PS2(µ-S)POS]·H2O 2.12 (b), 1.98 (t) 3.23, 3.39, 3.54 104.1 n/a ionic/iso 92

K2[C10H6PS2(µ-O)PS2] 1.95 (t) 3.35, 3.39 117.5 n/a ionic/iso 92

[Na{ArP(OtBu)S2}(THF)]∞ 1.97, 1.99 2.772–2.874 116.0 72.8 ionic/iso 93

pt
Na2[ArP(OtBu)(μ-S)S}2(DME)2] 1.97, 1.99 2.772–2.874 116.0 72.8 ionic/iso 93
ce
[K2{ArP(OtBu)(μ-S)S}2(THF)2]∞ 1.97, 1.98 3.16, 3.20, 3.22 117.0 63.7-106.2 ionic/iso 93

[K2{ArP(OtBu)(μ-S)S}2(DME)2]∞ 1.97, 1.98 3.16, 3.20, 3.22 117.0 63.7-106.2 ionic/iso 93

[Ti(MeCp)2O2S4(PAr)2] 1.94(t), 2.12(b) n/a 102.7, 103.5 n/a iso1 94

Ac

[Cr2(Cp)2(S2P(O)Ar)2] 2.03 2.37 102.8 83.9 iso 96

[Cr2(Cp*)2(S2P(O)Ar)2] 2.03 2.38 102.9 83.4 iso 96

[Cr2(Cp)(CO)3{S2P(Ar)(CO)2] 2.03 2.47 101.3 113.9* iso/chel 96

[Ru(cymene){ArP(O)S2}]2 2.03, 2.12 2.42, 2.43 99.0 86.7* aniso/chel 98

[Ru{S2PFc(OH)}2(PPh3)2] 2.00, 2.01 2.46, 2.55 102.5 n/a iso/chel 97

[Co{(S2PAr(OMe)}3] n/a 2.30-2.32 n/a 84.0 iso/chel 99

[Rh(cod)(Cp)Fe(C5H4PS2O<N3>)]2 2.00, 1.99 2.38, 2.42 n/a 83.5 iso/chel 100

[Ir{S2P(Fc)(OMe)}{COD}] 2.01 2.36, 2.37 102.5 82.9 iso/chel 101

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[Ni{S2(Ar)(OMe)}2] n/a 2.23, 2.24 n/a 88.7 iso/chel 99

an
[Ni{S2(Ar)(OMe)}2] 2.00 2.23, 2.24 102.7 88.8 iso/chel 105

[Ni{S2(Ar)(OEt)}2] n/a 2.22 n/a 88.04 iso/chel 99

M
[Ni{S2(Ar)(OiPr)}2] 2.00 2.22, 2.23 101.8 88.50 iso/chel 105

[Ni{S2(Fc)(OEt)}2] 2.00 2.23 101.2 88.13 iso/chel 108, 109

[Ni{S2(Fc)(OiPr)}2] 2.01 2.22 101.4 88.31 iso/chel 108

ed
[Ni{S2(Fc)(OBu)}2] 2.00 2.22 101.2 88.27 iso/chel 108

[Ni{S2(Ar)(OMe)}2(tptz)]
pt 1.96, 1.99, 2.00 2.38, 2.46, 2.57 102.2, 116.6 88.23 aniso/chel 112

[Ni{S2(Ar)(OMe)}2(py)2] 1.99 2.50 110.2 81.68 iso/chel 121

[Ni{S2P(Ar)(OMe)(ac-py)2] 1.99 2.47, 2.53 109.9 81.69 aniso/chel 122

ce
[Ni-Re heterobimetallic]3 1.99 2.47, 2.50 109.5 81.75 aniso/chel 126

[Ni2{S2P(Ar)(μ-O)}2(THF)2(H2O)2]2 2.04-2.10 2.21-2.27 96.7–97.7 n/a aniso 127

trans-[Pd{S2P(Ph)(OEt)}2] 2.00 2.34 103.3 84.4 iso/chel 1284

Ac

trans-[Pt{S2P(Ph)(OEt)}2] 2.02 2.34 100.7 83.5 iso/chel 1284

trans-[Pd{S2P(Ar)(OMe)}2] 2.01 2.34 104.5 85.7 iso/chel 129

trans-[Pt{S2P(Ar)(OMe)}2] 2.01 2.34 103.1 84.4 iso/chel 129

cis-[Pd{S2P(Ar)(OH)}2]·en·H2O 2.01 2.34 n/a n/a iso 130

trans-[Pd{S2P(Fc)(OEt)}2] 2.02 2.35 102.5 84.2 iso/chel 109

[Cu{S2P(p-C6H4OEt)(OMe)}{PPh3}2] 1.99 2.44, 2.50 112.4 84.17 iso/chel 134

[Cu2(ArS2P-O-PS2Ar)(PPh3)4] 1.99 2.36 117.4 n/a iso 135

[Cu4{Ar(S)2-P–O–P-(S)2Ar}2(dppa)2] 2.03-1.99 2.36-2.29 119.4 n/a aniso 135

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[Cu{(µ-S)(µ3-S)P(Fc)(OCH3)}]4 2.05, 1.99 2.29-2.24 n/a 105.0* aniso 138

an
[Ag{S2P(OMe)(4-C6H4OEt}{PPh2}]2 1.99, 2.02 2.53, 2.68 113.9 98.01 aniso 134

[Ag4{μ4-ArP(O)S2}2(dppm)4] 2.05 2.56-2.59 116.0 109.6 iso 141

M
[Ag28(μ6-S)2{ArP(O)S2}12(PPh3)12] 2.03-2.08 2.21-2.92 n/a n/a aniso 141

[Au(S2P(OH)Ph)2]Cl 2.05 2.34 98.2 83.5 iso/chel 144

[Au{S2P(OMe)(p-C6H4OEt}{PPh3}] 1.95, 2.06 2.32, 3.87 117.8 82.2 mono 134

ed
[Au{S2P(Ar)(OC5H9)]2 2.02 2.29, 2.30 116.8 171.4 iso 145

[Au{S2P(Ar)(OC5H9)}{PPh3}2]
pt n/a 2.85, 2.80 n/a 73.17 iso/chel 145

[Au2{SP(=S)(Ar)(OC5H9)}2(dppm)] 2.05, 1.95 2.31 n/a n/a mono 145

[Au2{SP(=S)(Ar)(OC5H9)}2(dppe)] 2.04, 1.94 2.32 114.3 n/a mono 145

ce
[Au2{SP(=S)(Ar)(OC5H9)}2(dppb)] 2.05, 1.95 2.30 n/a n/a mono 145

[Au{S2P(Ar)(OSiPPh3)}]2 2.01 2.29, 2.30 n/a 173.1 iso 149

[Au{S2PPh(OCH2CH=CH2)}]2 2.00 2.29, 2.30 117.3 172.4 iso 150

Ac

[Au{S2P(Ar)(Omenthyl)}]2 2.00 2.30 115.7 167.8 iso 152

[AuS2P(Fc){O(CH2)2O(CH2)2OMe}]2 2.02 2.30 118.0 176.09 iso 152

[Au{S2PPh(OC5H9)]2 2.00 2.30 115.7 169.0 iso 152

[Zn2{S2P(Ar)(OEt)}4] 2.00, 2.02 (2.32, 2.43)(2.31, 2.36) 108.6, 113.6 86.45 aniso 105

[Zn2{S2P(Ar)(OC5H9)}4] 2.00, 2.02 (2.34, 2.47)(2.32) n/a 85.5, 130.2 aniso 158

[Zn2{S2P(Fc)(OMe)}4] 2.00, 2.02 (2.37, 2.41)(2.31) 109.0, 114.5 86.01 aniso 120

[Cd2{S2P(Fc)(OMe)}4] 2.00, 2.02 (2.56, 2.65)(2.54) 110.8, 116.1 78.51 aniso 120

[Cd2{S2P(Ar)(OiPr)}4] 1.99, 2.02 (2.52, 2.66)(2.52) 111.1, 111.7 79.4 aniso 105

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[Cd2{S2P(Ar)(OtBu)}4] 1.99-2.04 2.51-2.98 111.3, 111.8 79.16, 106.9 aniso 93

an
[Hg2{S2P(Ar)(OEt)}4] 1.98, 2.04 (2.46, 2.78)(2.45, 2.62) 111.0, 114.8 78.1 aniso 105

[Hg2{S2P(Ar)(OiPr)}4] 1.99, 2.02 (2.49, 2.72)(2.49, 2.56) 110.6, 115.3 79.4 aniso 105

M
[Hg2{S2P(Fc)(OEt)}4] 1.97-2.04 (2.43, 2.89)(2.42) 112.4, 115.7 102.2 aniso 109

[Pb{S2P(Fc)(OEt)}2] 1.98, 2.01 (2.74, 3.01)(2.73, 2.85) 112.2, 113.3 73.5 aniso 109

[Pb{S2P(Fc)(OiPr)}2] 2.01, 1.99 (2.73, 2.94)(2.72, 2.95) 111.1, 111.3 72.4 aniso 120

ed
Notes:
A structural evaluation of 105 analysed Ni-S bonds containing [S2P(OR)2]¯, [S2PR2]¯, and [S2PR(OR’)]¯ ligands can be found in ref. 118.
pt
b = bridging, t = terminal, n/a = data either not available in original reference or not applicable.
1
based on similar Ti-O bond lengths (1.97, 1.98 Å), and S-P-O bond angles 107.5, 106.7°, respectively.
ce
2
Complete formula: Rh(CO)2[(C5H5)Fe(C5H4PS2OCH2C6H4N3)]
3
Complete formula: [Ni{S2P(Ar)(OCH2OCH2CH3)}2}{Re(4-pyCH2OCS2)(bipy)(CO)3}2].
3
cis-trans isomerism was demonstrated in solution.
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2.4 Synthesis methods

Why the [S2PR(OR’)]¯ type ligands were slow to develop is not immediately understood
since the commercial unavailability of key starting materials, inherent reactivity (especially

t
toward hydrolysis), and the potential toxicity these compounds and derivatives thereof exhibit, is

ip
not much different when compared to the well-established [S2PR2]¯and especially [S2P(OR’)2]¯
counterparts. The history of compounds formed from phosphorus and sulfur is very old. The first

cr
report of phosphorus sulfides was probably in 1740 when Marggraff described a fused mixture of

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phosphorus and sulfur, followed by distillation of the product [31]. From these efforts
tetraphosphorus decasulfide, P4S10, was synthesized by Berzelius in 1843 from white phosphorus
and sulfur [32]. P4S10 is a malodorous, pale yellow crystalline compound and plays a crucial role
an
in the development of dithiophosphonate chemistry. The first structures of P4S10 was proposed
by Mai (1911) [33] and Treadwell et. al. (1935) [34], but the correct structure was only obtained
M
31
in 1954 by Vos and Wiebenga [35]. The P NMR spectrum of solid P4S10 (Td point group)
shows a singlet at 45 ppm (relative to 85% H3PO4 (aq)), indicating that all P nuclei are
equivalent [36]. Reactions of P4S10 with organic reactants under a variety of reaction conditions
d

have an extensive patent literature [37]. Aromatic hydrocarbons such as anisole, phenetole,
e

xylene, naphthalene as well as thiophene [38] react with P4S10 to form 1,3-dithiadiphosphetanes.
pt

Dimeric crystalline products of general formula [RP(S)S]2 have been obtained from the reaction
between P4S10 and aliphatic [39] or aromatic [40] hydrocarbons. The reaction of P4S10 with
ce

ethanol was described in 1854 by Kekulé, a reaction that remains the most efficient way to
prepare diethyldithiophosphoric acid [41] and explains why dithiophosphate chemistry is much
better developed than dithiophosphonate chemistry, as the latter initially suffered serious
Ac

synthesis difficulties. Starting in 1945, Malatesta and Pizzotti described [Ni{S2P(Et)(OEt)}2] as

presumably the first metal dithiophosphonate complex [42,43], albeit in a manner difficult to
reproduce [44].

A key piece of the puzzle appears to lie with the development of dimers of the type [RP(µ-S)S]2
(R = aryl) which have traditionally been used by organic chemists to convert ketones into thiones

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and have first been reviewed by Maier in 1965 [45] and again in 1980 [46]. The preparation and
characterization of the phenyl-dimer [PhP(µ-S)S]2 was first described in 1962 [47,48] but the
procedure is not facile and requires the use of H2S gas introduced sub-surface at >210°C with
release of copious amounts of corrosive HCl as by-product, as shown in Scheme 1.

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Scheme 1. Synthesis of the phenyl-dimer [PhP(µ-S)S]2.

The analogues selenium dimer [PhP(µ-Se)Se]2, is known as Woollins’ Reagent (WR) and is
an
commercially available. WR cannot be prepared in a similar manner as the sulfur analogue. The
evolution and chemistry of WR has recently been described [49] and its chemistry as an
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excellent selenation reagent has been well developed [50-54]. The synthesis of the first stable
metadithiophosphonate had been described from reaction between RPR1R2 [R = 2,4,6-
(Me3C)3C6H2; R1 = R2 = H; R1R2 = CHNMe2] with S to give RP(S)(S), which gave
d

RP(OMe)(S)(SH) on treatment with MeOH [55].  

e
pt

A significant improvement came in 1978 when Lawesson and co-workers reported [56] the
reaction between anisole (phenetole is a useful alternative) and P4S10 which leads to the
ce

formation of dimer 2,4-bis(4-methoxyphenyl)-1,3-dithiadiphosphetane-2,4-disulfide, [(4-

MeOC6H4)P(µ-S)S]2. Here anisole acts as both the “solvent” and reactant which is convenient.
This dimer is known as Lawesson’s Reagent (LR) and is commercially available. The chemistry
Ac

of LR has been reviewed in 1985 [57,58] and 1993 [59] and 2003 [60] and extensively in 2007
[61]. Although the conversion of ketones into thiones still occupy the largest share of LR’s
utility, alcoholysis of LR yields the corresponding dithiophosphonic acid [62]. Reaction of LR
with carboxylic acid chlorides [63], esters, acetals, epoxides, sodium alkoxide, and thiols have
been reported [64-66]. A wide variety of alcohols can be utilized including unsaturated (allyl),
sterically demanding (adamantyl), and quasi-strained (cyclopentyl), in addition to reaction of LR

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Edited Oct 18 

with silanols and trialkylsilanols [67]. New P-S-N ring systems have also been developed from
naphthalene-based LR and its reaction with methylbis(trimethylsilyl)amine [68]. The preparation
of a solubilized form of LR and its thionation reactions have also been described [69] as well as
the reaction between LR and organonitrogen compounds [70]. A general perspective on organo-
P-S and P-Se heterocycles had been given [71,72]. One of us demonstrated that ferrocene, as an

t
ip
electron-rich organometallic with aromatic properties, can replace anisole and phenetole and
form the related [FcP(µ-S)S]2 or FcLR (Fc = ferrocenyl) type dimer [73]. The FcLR dimer has

cr
been used to form novel 1,2 thiaphosphetanes [74] P-S-N-type heterocycles [75,76], and
cycloaddition reactions with dienes, alkenes, and thioaldehydes [77]. The synthesis methodology

us
used to form these dimers and their subsequent reactions to form the ligand [S2PR(OR’)]¯ is
shown in Scheme 2. The ammonium or sodium salts can be readily treated with the appropriate
an
metal salts (chloride, nitrate, etc.) in aqueous or organic solvent. Removal of the unwanted salt
byproduct can be readily achieved through either filtration or solvent extraction.
M
e d
pt
ce
Ac

16 

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Edited Oct 18 

Scheme 2. Summary of synthesis methodology in forming either sodium or ammonium type

salts of [S2PR(OR’)]¯ R = 4-anisyl or ferrocenyl; R’ = primary or secondary alcohols.

A general method for the preparation of a wide variety of phosphonate derivatives, including
thiophosphonamides, thiophosphonates, and dithiophosphonates, from reduced phosphorus

t
intermediates was developed. Esters (or thioesters) of H-phosphinates were converted to highly

ip
reactive phosphonochloridites which react readily with alcohols, amines and thiols. After in situ
oxidation or sulfurization, phosphonate derivatives were isolated [78].

cr
Most recently, new complexes had been developed by an “anhydride route”, demonstrated in

us
Scheme 3, to form unusual Group 15/16 ligands in oligomeric and polymeric environments [79].

an
M
d

Scheme 3. Classical interpretation of the anhydride route through an insertion reaction of organic
e

anhydrides into the M-O bond of metal alkoxides (M = transition metal, R, R’ = organic group)
pt

shown above, and modern interpretation of reaction of the anhydride [RP(µ-E)E]2 with alkali
metal (M) alkoxides (E = S, Se; R = 4-anisyl, phenyl; R’=organic group) as shown below, after
ce

[79].

2.4 Oxidation products: bis(thiophosphonyl)disulfanes

Ac

Oxidation of [S2PR(OR’)]¯salts can readily be achieved with a mild oxidizing agent such
as I2 (with or without activated by KI) in aqueous or methanolic solution leading to disulfane
products of the type PR(OR’)(S)S-SPR(OR’)(S) (R = alkyl, aryl). As early as the 1970’s, diols
and polyols were used through cumbersome synthesis routes to form disulfanes [80,81]. New
products through the reaction of LR with diols led to stable diammonium salts [82], and they

17 

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Edited Oct 18 

were subsequently converted into disulfanes, but lack X-ray crystallographic analyses. The
reaction of bis(thiophosphoryl)disulfanes, and bis(thiophosphinyl)disulfanes with metal
compounds have been reviewed [83]. The corresponding bis(thiophosphonyl)disulfanes have not
been reviewed, but several oxidized S-S coupled compounds have been reported [84-87].

t
ip
2.5 Hydrolysis products and zwitterions

cr
Metal complexes of dithiophosphonates are susceptible to hydrolysis. For example, the

us
reaction between the dithiophosphonato dianion salt, (NH4)2[S2P(Fc)OCH2CH2O(Fc)PS2] and
[Au(PPh3)Cl] yields the complex [(PPh3)AuS2(Fc)P(OC2H4O)P(Fc)S2Au(PPh3)] [88].
an
However, the ligand gradually becomes oxidized, presumably due to moisture present in the
DCM solvent during crystal growth, resulting in substitution of a terminal P=S bond with a P=O
bond. A detailed mechanism for such hydrolysis reactions has not yet been proposed.
M
Zwitterions have been formed from the reaction between LR or FcLR and aminoalcohols, as
shown in Figure 1 [89-91].
e d
pt
ce

Figure 1. Zwitterion formed between FcLR and an aminoalcohol, after [89].

Ac

3.1 Group 1: alkali metals

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Edited Oct 18 

Kilian et al. reported novel condensed thionated bis(phosphonic) acid potassium salts
with a rigid naphthalene-1,8-diyl backbone [92], Figure 2. The backbone fixes the phosphorus
atoms in the sterically strained 1,8-positions of the naphthalene ring allowing bis(phosphonates)
to be isolated containing a P-X-P bridge built into six-membered C3P2X (X = S or O)
heterocycles. The largest structural change appears to be around the S-P-S bond angle between

t
ip
K2[C10H6PS2(µ-S)POS]·H2O at 104.1° and K2[C10H6PS2(µ-O)PS2] at 117.5°, the latter is the
norm for related K and Na salts, see Table 1.

cr
us
an
M
d

Figure 2. Condensed potassium salt derived from naphthalene, after [92].

e
pt

Rothenberger and co-workers reported a number of sodium and potassium salts [93] of the type
[Na{ArP(OtBu)S2}(THF)]∞ ,[Na2{ArP(OtBu)(μ-S)S}2(DME)2], [K2{ArP(OtBu)(μ-S)S}2(THF)2]∞
ce

and [K2{ArP(OtBu)(μ-S)S}2(DME)2]∞ (Ar = 4-anisyl). These compounds were all derived from
the reaction between LR and MOtBu (M = Na or K) in THF or DME. The generated
dithiophosphonato ligand in these reactions contain four donor centres which could all be
Ac

involved in metal bonding. The preparation of the alkali salts thus has a direct consequence on
the eventual supramolecular formation of the transition metal complexes, and allows
coordination of OtBu groups to metal atoms, a feature not previously observed.

3.2 Groups 2 and 3: alkali earth metals, Sc and Y.

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Edited Oct 18 

There appears to be no alkali earth or group 3 dithiophosphonate complexes reported.

This is in contrast to the well-developed dithiophosphates for similar metals [14].

3.3 Group 4: Ti, Zr, Hf

t
ip
Within this group, only two Ti dithiophosphonate complexes are known. Not

cr
surprisingly, in both cases the oxophilic nature of the Ti atom is apparent, in the first instance
[94] the Ti center bonds through the two O atoms of two ligands linked by a S-S bond in the

us
backbone (see section 2.3) as shown in Figure 3. This compound is derived from
(RCp)2TiS5(PAr)2 (contains a P-P bond in the backbone) which is highly labile and reactive
an
toward oxygen species whilst in contrast, the trithiophosphonate (RCp)2TiS5 species was
kinetically inert and resistent to a number of oxo compounds. In the other case the ligand forms
an O-P-S chelate with one S atom dangling [95], a tetra-aza ligand fills the other coordination
M
sites around the Ti atom.
e d
pt
ce

Figure 3. A neutral mononuclear Ti(IV) complex with a S-S backbone within a heterocycle, and
Ac

a kinetically inert trithiophosphonate.

3.4 Groups 5 and 6: V, Nb, Ta and Cr, Mo, W

Amongst these six metals, no group 5 dithiophosphonate complexes had been reported.
Surprisingly for the group 6 metals which readily binds sulfur, only three dimeric Cr complexes
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Edited Oct 18 

are known, all were obtained as a mixture of products (generally low yields) from the reaction
between [Cr2(Cp)2(CO)6] and LR, two of them are isomorphous, the one contains a Cp ring, the
other Cp*, see Table 1 [96]. One Cp complex forming two S-P-S chelates to each Cr atom is
shown in Figure 4. Clearly this area of research is ripe for further investigation.

t
ip
cr
us
an
Figure 4. A dimeric CpCr complex containing a S-P-S chelate, after [96].
M
3.5 Groups 7 and 8: Mn, Tc, Re and Fe, Ru, Os
d

Amongst these 6 metals, only Ru dithiophosphonate complexes have recently been

e

reported, all by Zhang and co-workers [97,98]. The Ru complexes vary from FcLR-based
mononuclear octahedral species, to dinuclear chelates, examples are shown in Figure 5. This
pt

group also shows a severe paucity of reported structures in contrast to the dithiophosphates
where all metals are well represented [14].
ce
Ac

21 

Page 20 of 47
Edited Oct 18 

t
ip
cr
us
an
Figure 5. Mono- (above) and dinuclear (below) octahedral Ru(II) complexes.
3.6 Group 9: Co, Rh, Ir
M
Group 9 metals are all represented, but have been developed only during the past decade.
All three metal complexes represent straightforward neutral S-P-S chelates. The cobalt(III)
d

complex is mononuclear with an octahedral geometry, [Co{(S2PAr(OMe)}3] [99]. The

rhodium(I) complex contains both a Fc-based S-P-S chelate and COD ligand [100] while the
e

iridium(I) complex is related to the Rh complex, [Ir{S2P(Fc)(OMe)}{COD}] [101].

pt
ce

3.7 Group 10: Ni, Pd, Pt

Ac

Group 10 is the best represented of all the groups, dominated by Ni(II) complexes in
particular, with Pd(II) and Pt(II) complexes also developed.

a. Nickel

The Ni(II) dithiophosphonate complex, [Ni{S2PPh(OEt)}2], was reported in 1967 by

Hartung [102] and presumably contains the first X-ray structural study for a complex with this
22 

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Edited Oct 18 

class of ligands. Many Ni(II) complexes of the similar neutral mononuclear type has since been
reported [99,103-106]. The use of diols of the type HO(CH2)nOH (n = 2-4) has become a popular
alternative and leads to the formation of dinuclear metal complexes [107]. Formation of Fc
moieties followed by replacing aromatics in complexes of the type [Ni{S2PFc(OR’)}2] where R’
= Et, iPr, etc. [108,109]. Aragoni et al. demonstrated that neutral Ni(II) complexes can be linked

t
ip
together with a variety of N-donor ligands such as pyridinyl-alkyne and pyridyl tetrazine [110]
and bipyridine or pyridinyl-1,4 diamine combinations [111] forming 6-coordinate Ni(II)

cr
polymeric type complexes in the process. An interesting variation of the polymeric species was
to include disulfide and trisulfide linkers between the pyridinyl ligands [112], as shown in Figure

us
6.

an
M
e d
pt

Figure 6. A 6-coordinate Ni(II) polymeric complex containing a pyridyl-trisulfide linker

ce

combination.
Ac

An anionic pentafluorophenylate ligand, commonly used to stabilize gold(I) centers [113], was
successfully utilized to form monoanionic Ni(II) complexes of the type
2-
[Ni{S2PAr(OMe)}{C6F5}2]¯ [114]. Dianionic complexes of the type [Ni{S2P(=O)(Et)}2] and
[Ni{S2P(=O)(Ar)}2]2- are also known [115,116] as well as the dianionic Fc derivative
[Ni{S2P(=O)(Fc)}2]2- all of which are stabilized by quaternary nitrogen salts [100]. Cationic
Ni(II) complexes are known containing one chelating dithiophosphonato ligand and a neutral
triaza macrocycle [117]. Other variations contain one anionic chelating dithiophosphonate,
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Edited Oct 18 

neutral water, and a tridentate nitrogen ligand [118]. The specially designed 2,4,6-tris(2-pyridyl)-
1,3,5-triazine-N,N’,N’’ ligand, shown in Figure 7, was successfully used to form a neutral Ni(II)
complex containing both a chelating and monoconnective S-dithiophosphonate and a cationic
Ni(II) complex where the dithiophosphonate ligand had been wholly displaced by a neutral
nitrogen ligand [106].

t
ip
cr
us
an
M
e d
pt
ce

Figure 7. Example of a neutral Ni(II) complex containing both a chelating and monoconnective
Ac

S bound dithiophosphonato ligand (above) and a cationic Ni(II) complex (below).

One of the key features of the dithiophosphonato ligand is that it is not symmetrical, and as a
result can give rise to isomers. In the majority of cases the trans isomer is formed with a
crystallographic inversion present in the molecule, but there are few exceptions for Ni(II) where
the cis isomer is formed. Thus, the P–N bond hydrolysis of an aminated LR and subsequent
reaction with NiCl2 led to the first example of Ni(II) dithiophosphonate complex with a cis
24 

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Edited Oct 18 

configuration; this complex was stabilised in the solid state by an extensive and intricate network
of hydrogen bonding involving the released ethylenediamine and a water molecule [119]. The
square planar Ni(II) complexes adopt two distinct configurations, trans with the ferrocenyl
groups above and below the square plane and cis with the ferrocenyl groups on the same side of
the square plane [120]; there is evidence to suggest that the isomerisation occurs via a cis-

t
ip
ML2(solv)2 intermediate, see Figure 8.

cr
us
an
Figure 8. Interconversion between cis/trans isomers in a square planar Ni(II) complex.
M
Addition of pyridine derivatives to trans-[Ni{S2PAr(OMe)}2] give rise to 6-coordinate Ni(II)
d

complexes of the type [Ni{S2PAr(OMe)}2(py)2], [121,122] where the py ligands are opposite
(trans) to each other in a virtual octahedral geometry. There are also rare examples where a
e

phenol derivative in [Ni{S2PAr(O-2,4-C6H3(tBu)2)}2] [123], a hydroxyl group in

pt

[Ni{S2PAr(OH)}2], which has the potential to be further deprotonated [124] and form a
‘complex of complexes’, and an alkyl group bound directly to the P atom in
ce

[Ni{S2PEt(OCH(CH3)2], have been described [125]. Luminescent heterometallic Ni/Re

complexes have also been reported [126], Figure 9.
Ac

25 

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Edited Oct 18 

t
ip
cr
us
Figure 9. An example of a luminescent heterometallic Ni/Re complex.
The majority of Ni(II) complexes are mononuclear with one example of an interesting
tetranuclear complex, as shown in Figure 10 [127]. an
M
e d
pt
ce

Figure 10. A tetranuclear Ni(II) complex containing 4- and 6-coordination around the metal
Ac

center, after [127].

There is also a rare example of a [Ni(en)3][SP(=S)Ar(OEt)]2 type complex, where the

dithiophosphonato ligand acts as a counter-ion not bound to a metal centre [99].

b. Palladium and Platinum

26 

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Edited Oct 18 

The first Pd(II) and Pt(II) dithiophosphonate complexes were 4-coordinate square planar
complexes, trans-[M{S2PPh(OEt)}2] (M = Pd, Pt) reported by Fackler and Thompson in 1981
[128]. The only structural difference between these complexes was the P-S bond distance for Pt
was slightly longer at 2.02 Å vs 2.00 Å, and the S-P-S bond angle slightly smaller at 100.7° vs
103.3°, respectively, when compared with the Pd complex. This was followed by the use of LR

t
ip
in the related complexes [M{S2PAr(OMe)}2] (M = Pd, Pt) reported by Aragoni et al. [129], later
replacing OR groups with OH groups forming a rare cis complex [130] and by replacing LR with

cr
FcLR [120,131]. There is also an interesting dinuclear Pd(II) complex reported containing a
bridging P-O-P moiety, Figure 11 [132].

us
an
M
e d
pt

Figure 11. A dinuclear Pd(II) complex derived from a FcLR dimer and containing a P-O-P
ce

bridge, after [132].

Ac

3.8 Group 11: Cu, Ag, Au

The dithiophosphonates of group 11 metals were reviewed in 2010 [133] and only the main
aspects will be summarized below with a discussion of new complexes that emerged since then.

a. Copper

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Edited Oct 18 

Mononuclear tetrahedral copper(I) dithiophosphonate complexes of the type [Cu{S2P(4-

C6H4OR)(OMe)}{PPh3}2] can be obtained from the reaction between [(Ph3P)2CuNO3] and
H[S2P(4-C6H4OEt)(OMe)] in nitrobenzene [134].
The copper(I) dithiophosphonate complex [Cu2(μ2ArS2P-O-PS2Ar)(PPh3)4], represents the

t
ip
only dinuclear Cu “dimeric” dithiophosphonate reported [135], and was obtained through LR
and CuOtBu in toluene, and dissolved upon addition of PPh3. Similarly, the tetranuclear complex

cr
[Cu4{Ar(μ2-S)2-P–O–P-(μ2-S)2Ar}2(dppa)2] formed through addition of dppa.
The tetranuclear cluster [Cu2(μ4-ArPS3)(PPh3)2]2 was formed from the reaction between LR,

us
CutOBu, and PPh3 [127]. The ring-opening of LR with CuOtBu under different conditions
showed that Cu(I) complexes can be produced selectively by judicious choice of the reaction
conditions. an
The structure of [Cu{S2P(4-C6H4OEt}(OR’)}2] (R’ = Me, Et) type complexes could be alluded
from spectroscopic and magnetic measurements [136], and the transport of Cu(II) ions through a
M
membrane was examined [137]. Recently, the reaction between Na[S2PFc(OMe)] and
[Cu(MeCN)4][ClO4] yielded the first tetranuclear Cu(I) dithiophosphonate cluster,
d

[Cu(OMe)Fc(μ-S)(μ3-S)]4, Figure 12 [138]. This unique structure contains trimetallic

triconnective and bimetallic diconnective coordination modes, the geometry around the Cu atoms
e

are trigonal pyramidal with S-Cu-S bond angles ranging from 107 to 129°. The Cu–S distances
pt

are not severely influenced by the different sulfur bridges, the Cu–S bond lengths are in the
narrow range of 2.24 to 2.29 Å. The average Cu–S bond length of 2.27 Å is shorter than those in
ce

tetra- and mononuclear trithiophosphonate tetrahedral copper(I) complexes at 2.43 Å [127] and
2.46 Å [93], respectively.
Ac

In comparing the mono-, di- and tetranuclear Cu(I) complexes, the following conclusions on
structure can be made. Firstly, the P-S bond lengths stay much the same at around 1.99Å in all
cases. In the tetranuclear case, however, the phosphorus atoms have a pseudo-tetrahedral
geometry, and the average P-µ-S bond of 1.99 Å remains whilst the average P-µ3-S bond of 2.05
Å is slightly longer. Secondly, the Cu-S bond lengths gradually decrease on going from
mononuclear average 2.44 Å, to dinuclear average 2.36 Å, to tetranuclear average 2.27 Å.

28 

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Edited Oct 18 

Thirdly, the S-P-S bond angles increase from mono- (112°), to di- (117°) to tetranuclear (119°)
Cu(I) complexes.

t
ip
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us
an
Figure 12. A unique tetranuclear dithiophosphonate Cu(I) cluster.
M
b. Silver
d

Only recently was the first mononuclear silver(I) dithiophosphonate complexes reported
e

[139,140]. The dinuclear silver(I) complex [Ag{S2P(OMe)(4-C6H4OEt}{PPh2}]2, contains an

pt

eight-membered Ag2S4P2 ring [134].

Metal salts with carboxylates or alkoxides proved useful to synthesize cluster complexes via the
ce

fragmentation of P–S bonds [79] as shown by the formation of the tetranuclear Ag(I) cluster
[Ag4{μ4-ArP(O)S2}2(dppm)4], Figure 13 [141].
Ac

29 

Page 28 of 47
Edited Oct 18 

t
ip
cr
Figure 13. A Ag4 cluster with terminal P=O bonds. Phenyl groups on dppm are omitted for

us
clarity.

an
The structure exists as a dimer of [Ag2{ArP(O)S2}(dppm)2] units. Both [ArP(O)S2]2- anions are
coordinated to four Ag atoms. Monodentate PPh3 (instead of dppm) was also used [141] and this
M
reaction revealed the cluster [Ag28(μ6-S)2{ArP(O)S2}12(PPh3)12], that can be considered a model
for bulk phase cation mobility [142]. This Ag28 cluster is related to the smaller Ag20 counterpart
prepared from the ultrasonic reaction of LR with Ag(OAc) and PPh3. The core of this cluster is a
d

Ag-based propeller comprised of one triangular central axis and three distorted rectangular fins.
e

The biconnective and triconnective P/S-containing ligands were generated from in situ P–S bond
cleavage and P–O bond formation process [143]. Similar to the copper complexes, the silver
pt

complexes show the same structural trends for key bond lengths and angles, see Table 1 for
ce

details.
c. Gold
Ac

The gold complex [Au{S2PPh(OH)}2]Cl, remains the first and only structurally characterized
mononuclear gold(III) dithiophosphonate complex [144]. A mononuclear gold(I)
dithiophosphonate complex [Au{S2P(OMe)(p-C6H4OEt}{PPh3}], was reported [134]. Another
type of mononuclear gold(I) complex was obtained through the reaction between the dinuclear
complex [AuS2P(4-C6H4OMe)(OC5H9)]2, and PPh3 (molar ration 1:4) in CH2Cl2 solution leading
to complex [Au{S2P(4-C6H4OMe)(OC5H9)}{PPh3}2] [145]. Related dinuclear complexes such as

30 

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Edited Oct 18 

[Au2{SP(=S)(Ar)(OC5H9)}2(dppm)] and [Au2{SP(=S)(Ar)(OC5H9)}2(dppb)] are unique as they

are rare examples of dinuclear Au(I) complexes showing monobidenticity as clearly observed
from structural investigation with P-S bond lengths at 2.05 Å, and the shorter terminal P=S bond
length at 1.95 Å. Characterized dinuclear gold(I) dithiophosphonate complexes of the type
shown Scheme 4 are intensely studied because they provide a framework for the study of weak

t
ip
inter- and intramolecular interactions between closed-shell gold(I) atoms [146-149]. However,
high nuclearity dithiophosphonate clusters is yet to be achieved for gold.

cr
us
an
M
e d
pt
ce

Scheme 4. Common 8-membered gold(I) metallacycles forms two possible isomers.

Dinuclear gold(I) dithiophosphonate complexes shows the trans (or anti) configuration in the
Ac

solid state exclusively. Solid-state magic-angle-spinning 31P NMR also confirms the trans isomer
to be the sole product in bulk form. Solution 31P NMR indicate both trans and cis forms exist in
solution. A significant number of dinuclear gold(I) dithiophosphonate complexes had been
reported [149-152], the complex [Au{S2P(4-C6H4OMe)(OSiPh3)}]2 shows a rare example of a
M-S-P-O-Si-C heteroatom chain (M = transition metal) [149]. The complex
[Au{S2PPh(OCH2CH=CH2)}]2, introduced unsaturation into the ligand with an allyl moiety
[150], and had been subjected to a detailed theoretical studies [151].
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Menthol is a chiral natural product containing an alcohol functionality and was used to form
[Au{S2P(4-C6H4OMe)(O-menthyl)}]2, (menthyl = dehydroxylated menthol) [152]. The complex
[Au{S2PFc(O(CH2)2O(CH2)2OMe)}]2, represents an example where FcLR was utilized to
complex a transition-metal center [152]. A host of other transition metals have since utilized
FcLR [120]. The strongly luminescent complex [Au{S2PPh(OC5H9)}]2 shows very short inter-

t
ip
and intramolecular Au···Au interactions [152]. The complex has a layered crystal packing motif
that can potentially intercalate volatile organic compounds (VOC’s) into the structure and alter

cr
the luminescence properties. Such ‘solvoluminescent’ compounds have been studied extensively
[153-155]. The direct reaction of FcLR with [Au2Cl2(dppm)], in THF forms a trithiophosphonate

us
[149] whilst reaction with ClAuPPh3 forms mononuclear chelating complexes of the type
[Au{S2P(OH)Fc}(PPh3)], or reaction with [PPN][AuCl2] forms dinuclear complexes of the type
an
[Au2{S2P(OH)Fc}2][N(PPh3)2]Cl, [132]. Since the first example of using a chiral alcohol had
been reported [152], a number of similar complexes had been demonstrated [156].
M
3.9 Group 12: Zn, Cd, Hg
d

The complexes of zinc(II) dithiophosphonates reported to date are structurally

e

remarkably similar (Figure 14, Table 1), all are 4-coordinate and dinuclear in nature with one
pt

ligand S-P-S chelating and the other bridging through the S atoms. The complexes contain OR’
groups derived from simple alcohols, and R groups vary between 4-anisyl [105,107,157,158]
ce

and 4-phenityl [159] and ferrocenyl [120]. The P-S bond lengths in all cases vary by a small but
discernible amount ie 2.00 and 2.02 Å, the Zn-S bond lengths vary between 2.32 and 2.43 Å for
the chelating ligand and between 2.31 and 2.36 Å for the bridging ligand, clearly indicative of an
Ac

anisobidentate bonding mode in all cases. The only exception to these complexes is a
mononuclear coordination polymer containing two monoconnective S-bound moieties as well as
derivatized bipyridine ligands [160].

32 

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Edited Oct 18 

t
ip
cr
Figure 14. A classic example of a 4-coordinate Zn(II) dithiophosphonate complex showing
different coordination modes around metal centers. The ligand is anisobidentate in both

us
coordination modes.

The cadmium complexes are closely related to the zinc(II) complexes being dinuclear, but
an
because of the larger atom size, the metal can accommodate larger coordination numbers.
Although dinuclear 4-coordinate complexes are found [120] most are 5-coordinate containing
M
two S-P-S chelates and a triconnective mode with an S-atom bridging two metal centers
[93,105,161]. There are also rare examples of mononuclear 6-coordinate coordination polymers
containing two S-P-S chelating dipyridine derivatives [162,163]. There are only a handful of
d

mercury complexes reported and more development is needed. All the complexes are structurally
e

more or less similar, as shown in Figure 15. The complexes are all mercuric, neutral, and 4-
pt

coordinate [105,109,164]
ce
Ac

Figure 15. A dinuclear Hg(II) complex derived from FcLR.

33 

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3.10 Group 13: B, Al, Ga, In, Tl

Complexes of these elements have not been reported except an Al(III) complex that lacks
X-ray crystallographic analysis [165].

t
ip
3.11 Group 14: C, Si, Ge, Sn, Pb

cr
There is a large number of reported crystal structures of dithiophosphonates that are

us
esters of the type SP(=S)(OR’)(R) (where R’ ≠ H) [89,166-177], and as a result is no longer a
convenient ligand as far as coordination chemistry is concerned since the Lewis basicity is vastly
an
reduced. Silicon [178] and organosilicon [179] compounds are also known but without X-ray
analyses. A mononuclear 4-coordinate germanium complex, [Ge(CH3)2{SP(=S)Ar(OSiPh3)}2]
has been reported [180] and a number of others, but without X-ray structure [181]. The 5-
M
coordinate mononuclear tin complex [SnClPh2{S2PAr(OEt)}] has been described [180] as well
as dimethyl complexes related to the Ge complex above [180], and others [181,182]. Lead had
d

been developed with all the complexes being mononuclear and neutral of the type
[Pb{S2PFc(OR)}2] containing two S-P-S chelates [109,120] or as coordination polymers [105],
e

and others [183].

pt

3.12 Group 15: N, P, As, Sb, Bi

ce

Nitrogen is in all cases coordinated as an ammonium or quaternary amine salt [100,

Ac

184,185], including the salt of cholesteryl, as shown in Figure 16 [186].

34 

Page 33 of 47
Edited Oct 18 

t
ip
cr
Figure 16. The P/S functionalization of the OH moiety in the steroid cholesterol, after [186].

us
The preparation of hydrated ammonium salts of the dithiophosphonic acids
(RC6H4CH2O)(Fc)P(S)(SH) [R=3-(PhCH2O, 4-Bu] had been reported [187]. Phosphorus is
an
similarly mostly coordinated as a phosphonium salt [92]. There are a number of As, Sb and Bi
complexes reported, but none with X-ray analysis. These organometallic derivatives have been
M
prepared directly from the LR with metal alkoxides [183,188,189].
d

3.13 Groups 16-18 and lanthanides

e

Complexes of these groups have not been reported.

pt
ce

4. 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
Ac

expected. The scope shown here amongst 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 soluble/stable analogues has not yet been
reported, nor mixed P/S/Se/Te analogues, and their respective mixed chalcogen-chalcogen (eg. -
S-Se- or -S-Te-) oxidized coupling reactions. Development of reactivity trends can be expected,

35 

Page 34 of 47
Edited Oct 18 

especially toward catalyst design or dehydrosulfurization reactions. The FcLR derivative proves
useful in extending this chemistry, and inevitably one wonders if other metallocenes or
organometallics in general be considered to perform the same function? Moving toward
nanomaterials, one feature that had been well demonstrated by proof-of-concept is the design of
related dithiocarbamato ligands and direct attachment thereof to Au nanoparticle (AuNP)

t
ip
surfaces [190,191]. There is no reason why this feature cannot also be exploited by the
dithiophosphonato ligands in the near future.

cr
Acknowledgement

us
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.
an
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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. 

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