Dithiophosphate Ligands Research Articles

A hexanuclear gold(i) metallatriangle derived from a chiral dithiophosphate: synthesis, structure, luminescence and oxidative bromination reactivity

We report the synthesis, structure, luminescence and reactivity of a 27-membered gold(I) metallatriangle containing three separate dinuclear gold(I) units self-assembled from a chiral tetradentate dianionic dithiophosphate ligand. The hexanuclear complex luminesces in the solid-state (λmax = 488 nm) at 298 K. Additionally, the Au(I) complex forms an unexpected dinuclear Au(III) oxidative addition product upon reaction with Br2.

Catena-Poly[[[O,O′-bis(2-methylphenyl) dithiophosphato-κ2S,S]lead(II)]-μ-O,O′-bis(2-methylphenyl) dithiophosphato-κ3S,S′:S

In the title compound, [Pb(C14H14O2PS2)2]n, the metal atom is surrounded by two O,O′-bis­(2-methyl­phen­yl) dithio­phosphate ligands bonding through the S-donor atoms. Three of the Pb—S bond lengths are are close to each other at 2.7710 (18), 2.8104 (16) and 2.8205 (16) Å, while the fourth Pb—S bond is elongated at 3.0910 (18) Å and reflects the fact that this atom is involved in inter­molecular bridging to an adjacent PbII atom [Pb—S = 3.145 (2) Å]. The bond angles demonstrate that the PbII atom contains a stereochemically active lone pair with a distorted octa­hedral geometry about the PbII atom. This distortion is shown by the S—Pb—S bite angles of 73.63 (4) and 69.50 (4)°, while the remaining S—Pb—S angles range from 81.03 (5) to 143.66 (5)°. One of the benzene rings shows positional disorder over two orientations with occupancy factors of 0.747 (11) and 0.253 (11).

Synthesis and Characterization of O,O'-Bis(α-Naphthyl, β-Naphthyl, and 2, 3, 5-Trimethylphenyl)Dithiophosphate Ligands

O,O′-Bis(α-Naphthyl, β-Naphthyl and 2,3,5-trimethylphenyl) dithiophosphate ligands have been isolated as triethylammonium salts, (α-C10H7O-, β-C10H7O, and (CH3)3C6H2O)2PS2HNEt3, by the reaction of α-C10H7OH, β-C10H7OH, or (CH3)3C6H2OH with P2S5 in presence of Et3N, in 4:1:2 molar ratio in chloroform under anhydrous conditions. Acidic form of these ligands, (α-C10H7O-, β-C10H7O-, or (CH3)3C6H2O)2PS2H, have been obtained by the direct reaction of α-C10H7OH, β-C10H7OH-, or (CH3)3C6H2OH with P2S5 in 4:1 molar ratio in presence of microwaves under solvent-free conditions. Both forms of the ligands have been converted into corresponding sodium salts, (α -C10H7O-, β-C10H7O-, or (CH3)3C6H2O)2PS2Na. These compounds have been characterized by elemental analyses (C, H, N, and S) and mass, IR, and NMR (1H, 13C and 31P) spectroscopic studies. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

Synthesis, structure and characterization of new stibocanes substituted with dithiophosphate ligands

Four new stibocanes substituted with cyclic dithiophosphate ligands O(CH2CH2S)2SbS2P(OCH2)2CEt2 (1), O(CH2CH2S)2SbS2P(OCH2)2C(Me)Pr (2), S(CH2CH2S)2SbS2P(OCH2)2CEt2 (3) and S(CH2CH2S)2SbS2P(OCH2)2C(Me)Pr (4) were prepared from the corresponding chloro oxa- and thia-stibocanes and the sodium salt of the dithiophosphoric acids 5,5-diethyl-(2-mercapto-2-thiono-1,3,2-dioxaphosphinane) and 5-methyl-5-propyl-(2-mercapto-2-thiono-1,3,2-dioxaphosphinane) in ethanol. The compounds obtained were characterized by IR, EI-MS and multinuclear NMR (1H, 13C, 31P) spectroscopies. The single-crystal structures of 1 and 2 were determined which show the presence of three types of secondary bonding: i.e. strong Sb---O transannular interactions of 2.607(4) and 2.600(4)Å, respectively, anisobidentate coordination of the ligand (exocyclic chelation) average Sb---S distance 3.355Å and intermolecular interactions that lead to supramolecular associations. The coordination geometry around antimony atom in both 1 and 2 can be described as Ψ tricapped trigonal bipyramidal AB4CD2E. The eight membered ring presents a boat-chair conformation in both compounds and the 1,3,2-dioxaphosphinane ring has the chair conformation, with the stibocane in the axial position.

Synthesis and Characterization of O,O’-(o-, m-, p-Ditolyl/dibenzyl/diphenyldithiophosphate) Complexes with Cobalt

Tris(O,O′-ditolyl/dibenzyl/diphenyldithiophosphato)cobalt(III) complexes (1–5) were synthesized by the reaction of CoCl2·6H2O and NH4S2P(OR)2. Initially, the bis(O,O′-ditolyl/dibenzyl/diphenyldithiophosphato)cobalt(II) complexes were formed, oxidized to their analogous tris complexes. In this study, oxidation rate of individual dithiophosphate ligand were investigated on the basis of physical changes. Cobalt(III) complexes (1–5) were characterized by elemental analyses, conductivity measurement, TGA/DSC, and spectroscopic techniques (infrared [IR], ultraviolet [UV]-visible, 1H-, 13C-, and 31P-NMR, mass). The experimental results suggest that these complexes have distorted octahedral geometry with bidentate chelation dithiophosphate moieties. Molecular weight determinations of these complexes indicate their monomeric nature.

Crystalline O, O′-di- sec-butyl and O, O′-diethyl dithiophosphate platinum(II) complexes: Synthesis, 13C and 31P CP/MAS NMR, single crystal X-ray diffraction studies and thermal behaviour

Crystalline bis( O, O′-di- sec-butyldithiophosphato)platinum(II) was prepared and studied by means of 13C, 31P CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. The unit cell of the platinum(II) compound is comprised of one centrosymmetric mononuclear molecule [Pt{S 2P(O- sec-C 4H 9) 2} 2], in which the dithiophosphate groups display structural equivalence in both 31P NMR and XRD data. A pair of the dithiophosphate ligands exhibit the same S, S′-bidentate chelating structural function and form two planar four-membered chelate rings, [PtS 2P], in this molecule. The planar configuration of the [PtS 4] chromophore in structure 1 is governed by the dsp 2-hybrid state of platinum(II). The structural states of the dithiophosphate groups in two different samples of complex 1 (one crystallised from ethanol and the other one precipitated from an aqueous solution) are all characterised by almost rhombic 31P chemical shift tensors. The observed essential dispersion of the 31P NMR chemical shift is caused by a coexistence of six optical isomers of molecule 1. The thermal behaviour of this compound was studied by means of simultaneous thermal analysis (a combination of TG and DSC) under an argon atmosphere. The thermal behaviour shows that the mass of 1 is lost in three steps, involving successive thermal decompositions of the organic and inorganic parts of this compound with platinum(II) dithio- meta-phosphate and reduced metallic platinum as the intermediate and the final products, respectively.

Synthesis and spectroscopic characterization of eleven mixed-ligand diorganotellurium(IV) compounds containing dithiocarbamate and dithiophosphate ligands

Eleven mixed-ligand organotellurium(IV) compounds of composition R 2Te(dtc)(dtp) have been prepared employing two different dithiocarbamate (dtc) and dithiophosphate (dtp) ligands: 1, R 2 = C 4H 8, dtc = S 2CNEt 2, dtp = S 2P(OCH 2) 2CEt 2; 2, R 2 = C 8H 8, dtc = S 2CNEt 2, dtp = S 2P(OCH 2) 2CEt 2; 3, R 2 = C 4H 8O, dtc = S 2CNEt 2, dtp = S 2P(OCH 2) 2CEt 2; 4, R 2 = C 5H 10, dtc = S 2CNEt 2, dtp = S 2P(OCH 2) 2CEt 2; 5, R 2 = C 4H 8, dtc = S 2CN(CH 2) 4, dtp = S 2P(OCH 2) 2CEt 2; 6, R 2 = C 8H 8, dtc = S 2CN(CH 2) 4, dtp = S 2P(OCH 2) 2CEt 2; 7, R 2 = C 4H 8O, dtc = S 2CN(CH 2) 4, dtp = S 2P(OCH 2) 2CEt 2; 8, R 2 = C 5H 10, dtc = S 2CN(CH 2) 4, dtp = S 2P(OCH 2) 2CEt 2; 9, R 2 = C 4H 8, dtc = S 2CN(CH 2) 4, dtp = S 2P(OCH 2) 2CMe nPr; 10, R 2 = C 8H 8, dtc = S 2CN(CH 2) 4, dtp = S 2P(OCH 2) 2CMe nPr; 11, R 2 = C 4H 8O, dtc = S 2CN(CH 2) 4, dtp = S 2P(OCH 2) 2CMe nPr. 1– 11 were characterized by mass spectrometry, IR spectroscopy and multinuclear NMR ( 1H, 13C, 31P, 125Te) spectroscopy. The molecular structures of 2, 4 and 6, of which 2 crystallized in form of two different polymorphs ( 2a and 2b), were analyzed by single-crystal X-ray diffraction analysis. This analysis showed that the coordination mode of both ligand types is anisobidentate. When considering only covalent Te–C and Te–S bonds, the coordination geometry of the tellurium atoms is distorted Ψ-trigonal-bipyramidal, since the lone pair is stereochemically active and occupies an equatorial position together with the carbon atoms of the tellurocycles. If secondary Te⋯S interactions are considered also, the coordination sphere around tellurium is best described as bicapped Ψ-trigonal-bipyramidal for the complexes with two intramolecular Te⋯S secondary bonds and monomeric molecular structures, and pentagonal-bipyramidal for the complexes in which neighboring molecules in the crystal lattice are linked through additional weak intermolecular Te⋯S secondary bonds to form dimeric supramolecular aggregates.

Supramolecular Self-Organization in Mercury(II) Dicyclopentyldithiophosphate Polynuclear Complex

In the monomeric unit [Hg(μ-S2P(OCp)2) (S2P(OCp)2)] (Cp = cyclopentyl) moiety, the one dithiophosphate ligand acts as a chelating ligand and the other one acts as a bridging ligand by their sulfur atoms. The monomeric units arrange in order to give rise to an infinite polymeric structure along the direction of the b axis by the two-fold screw axis. The compound displays a supramolecular self-organization in the solid state through the additional Hg····S (3.516 Å) secondary interactions with formation of chain-like polymeric arrays. Also, there are some weak intra- and intermolecular hydrogen bonds between some of the hydrogen atoms of Cp and S atoms. The intermolecular hydrogen bonds form infinite polymeric chains that lie along the b axis, to each other, and along the c axis to contribute to the supramolecular association. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

Polymeric thallium(I) O,O′-diisopropyl dithiophosphate [Tl{S2P(O-iso-C3H7)2}] n : Synthesis, structure, and 13C and 31P CP/MAS NMR spectra

The crystalline polymeric thallium(I) O,O′-diisopropyl dithiophosphate [Tl{S2P(O-iso-C3H7)2}] n (I) was obtained and examined by solid-state 13C and 31P CP/MAS NMR spectroscopy. Diagrams of the χ2 statistic were constructed from the complete 31P MAS NMR spectra and used to calculate the 31P chemical shift anisotropy (δaniso = (δ zz − δiso)) and the asymmetry parameter (η = (δ yy − δ xx )/(δ zz − δiso)). The 31P chemical shift tensor has a nearly axial symmetry (η = 0.22, δ zz < δ yy ≈ δ xx ). The MAS NMR spectral patterns correspond to the negative sign of δaniso (δ zz < δ yy < δ xx ), which indicates bridging or chelating-bridging coordination of the dithiophosphate ligands (Dtph). X-ray diffraction analysis revealed a polymeric structure of compound I. The polymer chain consists of alternating mononuclear [Tl{S2P(O-iso-C3H7)2}] molecules with opposite spatial orientations. The Dtph ligands are coordinated in a mixed, chelating-μ3-bridging fashion. The shape of the 31P NMR signal was interpreted in terms of the 31P-203,205Tl coupling pattern proposed from crystallographic data.

Catena-Poly[[bis(O,O′-diisopropyl dithiophosphato-κ2S,S′)nickel(II)]-μ-bis(4-pyridylmethylene)diazane-κ2N:N′

The Ni atom in the title linear supra­molecular polymer, [Ni(C6H14O2PS2)2(C12H10N4)]n, exists within a trans-N2S4 octa­hedral donor set defined by two symmetrically coordinating dithio­phosphate ligands and pyridine N atoms derived from two bridging bis­(4-pyridylmethyl­ene)diazane ligands. The Ni atom lies on a centre of inversion and the bis­(4-pyridylmethyl­ene)diazane ligand is also disposed about a centre of inversion. The chains are arranged into layers sustained by C—H⋯S contacts and inter­digitate with neighbouring layers, forming the crystal structure.

Alkylation of a Dimolybdenum SO Bridge, Subsequent Reactions, and Characterization of the Thioperoxide Bridge

The SO bridge of the complex, [Mo(2)(NTo)(2)(S(2)P(OEt)(2))(2)(mu-O(2)CMe)(mu-SBn)(mu-SO)], 1, displayed nucleophilicity at O, giving alkylation products [Mo(2)(NTo)(2)(S(2)P(OEt)(2))(2)(mu-O(2)CMe)(mu-SBn)(mu-SOR)](+), 4(+), which contained the thioperoxide bridge. These cations were then subject to nucleophilic attack by two pathways. Debenzylation of the bridge thiolate in 4(+) afforded neutral [Mo(2)(NTo)(2)(S(2)P(OEt)(2))(2)(mu-O(2)CMe)(mu-S)(mu-SOR)], 5; de-esterification of a dithiophosphate ligand in 4(+) gave [Mo(2)(NTo)(2)(S(2)P(O)(OEt))(S(2)P(OEt)(2))(mu-O(2)CMe)(mu-SBn)(mu-SO)], 6, which contained a monoester, dithiophosphate ligand. Complex 1 gave a slow and clean reaction in the crystalline state, further demonstrating its nucleophilicity by attacking a neighboring molecule in its lattice. X-ray crystallography confirmed the thioperoxide linkage and revealed structural similarities of the Mo(2)(mu-SOR) unit to sulfenate esters (RSOR) and related derivatives.

Facile Entrapment of a Hydride inside the Tetracapped Tetrahedral CuI8Cage Inscribed in a S12Icosahedral Framework

Reaction of [Cu(CH(3)CN)(4)](PF(6)) and NH(4)[S(2)P(OR)(2)] in a 4:3 ratio in acetone at room temperature produces octanuclear dicationic copper complexes [Cu(8){S(2)P(OR)(2)}(6)](PF(6))(2) (R = (i)Pr, 1; Et, 3) in 81 and 83% yields, respectively. On the other hand, reaction of [Cu(CH(3)CN)(4)](PF(6)), NH(4)[S(2)P(OR)(2)], and NaBH(4) in an 8:6:1 molar ratio in THF for 1 h yields [Cu(4)(H)(mu(3)-Cu)(4){S(2)P(OR)(2)}(6)](PF(6)) (R = (i)Pr, 2a; Et, 4a) in 87 and 82% yields, respectively. In a similar reaction when NaBD(4) is used instead of NaBH(4), [Cu(4)(D)(mu(3)-Cu)(4){S(2)P(OR)(2)}(6)](PF(6)) (R = (i)Pr, 2b; Et, 4b) are obtained in 83 and 78% yields, respectively. Structural elucidations of 2a and 4a reveal the tetracapped tetrahedral Cu(8) cage with an interstitial hydride. Each of the Cu(I) centers is trigonally coordinated by three S atoms, and each of the six dithiophosphate ligands is connected to a Cu(4) butterfly, where the hinge positions are occupied by two copper atoms situated at the vertex of the central tetrahedron and the wingtips are two capping Cu atoms. The 12 S atoms out of the six ligands constitute an icosahedron around the hydride-centered tetracapped tetrahedral Cu(8) framework. Surprisingly, empty Cu(8) clusters 1 and 3 can abstract hydride (or deuteride) from NaBH(4) (or NaBD(4)) in THF to form 2a and 4a (or 2b and 4b), respectively. Apparently the cubic Cu(8) core, which is known to be formed in the reaction of Cu(I) salt and dichalcogenophosph(in)ate ligands, undergoes a tetrahedral contraction due to the strong Cu...H interactions. Interestingly, the chloride can also be replaced from the chloride-centered Cu(8) complex of [Cu(8)(Cl){S(2)P(OEt)(2)}(6)](PF(6)) by hydride (or deuteride) to form 2a and 4a (or 2b and 4b). However, the hydride- and deuteride-centered compounds 2a,b and 4a,b do not allow the guest exchange.

Alkoxo-Bridged Heterobinuclear Derivatives of Arsenic(III) and Boron Based on Dithiophosphate Ligands: Synthesis and Characterization

The heterobinuclear derivatives of arsenic(III) and boron of the general formula [(RO)2P(S)S]2As(μ -OPri)2B(OPri)2 where R = Me(1); Et (2); Pri (3); Prn (4); and Bun (5)] have been synthesized by the reactions of chlorobis(dialkyldithiophosphato)arsenic (III) compounds, [(RO)2P(S)S]2AsCl with sodium tetraisopropoxoborate, NaB(OPri)4 in 1:1 molar ratio in refluxing benzene solution. All these new nonvolatile, moisture-sensitive, light-yellow colored, viscous liquid derivatives have been characterized by elemental analyses and molecular weight measurements. Their FT IR, multinuclear NMR (1H, 13C, 31P, and 11B), and FAB mass spectral studies have been discussed.

Synthesis, structural and multinuclear natural abundance (13C, 31P, 195Pt) CP/MAS NMR studies of crystalline O,O′-dialkyldithiophosphate platinum(II) complexes

Platinum(II) O,O′-dicyclohexyl dithiophosphate [Pt{S2P(O-cyclo-C6H11)2}2] (I) and platinum(II) O,O′-diisopropyl dithiophosphate [Pt{S2P(O-iso-C3H7)2}2] (II) complexes were obtained and studied by solidstate 13C, 31P, and 195Pt CP/MAS NMR spectroscopy. The dithiophosphate (Dtph) ligands in molecular structure I were found to be coordinated by platinum in S,S′-bidentate fashion to form the planar chromophore [PtS4] (single-crystal X-ray diffraction data). For complex II, a new α-form (α-II) was obtained and identified by 31P MAS NMR spectroscopy. The 31P chemical shift anisotropy δaniso and the asymmetry parameter η of the 31P chemical shift tensor were calculated from the whole MAS spectra.

Tetraphenylantimony(V) O,O′-dialkyl dithiophosphates [Sb(C6H5)4{S2P(OR)2}] (R = s-C4H9, c-C6H11): Synthesis, structures, and 13C and 31P CP/MAS NMR spectra

Tetraphenylantimony(V) O,O′-di-sec-butyl dithiophosphate (I) and tetraphenylantimony(V) O,O′-dicyclohexyl dithiophosphate (II) [Sb(C 6H5)4{S2P(OR)2}] (R = sec-C4H9 or cyclo-C6H11) were obtained. Th ...

Reactivity of Arsenic Trichloride and Glycolates with O,O′‐bis(ortho‐, meta‐ or para‐tolyl) Dithiophosphates

Reactions of arsenic trichloride and 2‐chloro‐1,3,2‐dioxarsolane or ‐dioxarsinane, sC1 (G=-CH2CH2- or -CH2CH2-CH2-), with sodium salt of O,O′‐bis(ortho‐, meta‐ or para‐tolyl) dithiophosphate ligands, (o‐, m‐ or p‐ MeC6H4O)2PS2Na, in different molar ratio in toluene under anhydrous conditions results in the formation of complexes corresponded to [{(o‐, m‐ or p‐MeC6H4O)2PS2}nAsCl3‐n] (n=1 or 2) and [(o-, m- or p- MeC6H4O)2 (n=2 or 3) in 83–93% yield. These yellow complexes were characterized by elemental analysis, molecular weight determinations, IR and NMR (1H, 13C and 31P) spectroscopic studies, which revealed monomeric nature of the complexes and anisobidentate mode of bonding of dithio moiety with arsenic atom, leading to a trigonal bipyramidal or octahedral geometry.

Bis(O,O′-diisopropyl dithiophosphato-κ2 S,S′)(1,10-phenanthroline)nickel(II)

The Ni atom in the monomeric title compound, [Ni(C6H14O2PS2)2(C12H8N2)], is within a distorted octahedral N2S4 geometry, defined by two chelating dithiophosphate ligands and a chelating 1,10-phenanthroline ligand.

Synthesis and characterization of binuclear oxomolybdenum(V) and dioxomolybdenum(VI) O, O′-ditolyl dithiophosphate complexes. : Crystal structures of Mo 2O 3[S 2P(OC 6H 4Me- o) 2] 4, Mo 2O 3[S 2P(OC 6H 4Me- m) 2] 4 and MoO 2[S 2P(OC 6H 4Me- p) 2] 2

A series of binuclear oxomolybdenum(V) O, O′-ditolyl dithiophosphate complexes, Mo 2O 3[S 2P(OR) 2] 4 (R = o-, m-, p-C 6H 4Me) were synthesized by drop wise addition of aqueous solution of the ammonium salt of O, O′-ditolyl dithiophosphoric acid into an acidic solution of sodium molybdate with constant stirring to yield purple solids. Dioxomolybdenum(VI) O, O′-ditolyl dithiophosphate complexes, MoO 2[S 2P(OR) 2] 2 (R = o-, m-, p-C 6H 4Me and CH 2C 6H 5) were also synthesized by reducing Mo 2O 3[S 2P(OR) 2] 4 with OPPh 3 in benzene to yield yellow solids. These complexes were characterized by elemental analysis and IR, 1H and 31P NMR spectroscopy and, in three cases, by X-ray crystallography. In Mo 2O 3[S 2P(OC 6H 4Me- o) 2] 4 and Mo 2O 3[S 2P(OC 6H 4Me- m) 2] 4, the environment around each molybdenum atom can be described as the expected distorted octahedral, consisting of one terminal and one bridging oxygen along with the four chelating sulfur atoms of the dithio ligands, with one Mo–S distance being significantly longer than the other three. In MoO 2[S 2P(OC 6H 4Me- p) 2] 2 the geometry around the Mo atom is again distorted octahedral with two cis terminal oxygen atoms and two anisobidentate dithiophosphate ligands.

Synthesis and Characterization of O,O′-(o-, m-, or p-Ditolyl) Dithiophosphate Ligands

O,O ′-(ortho-, meta-, or para-ditolyl) dithiophosphate ligands have been isolated as triethylammonium salts, (o-, m-or p-CH 3 C 6 H 4 O) 2 PS 2 HNEt 3 , by an auto-catalytic reaction of cresols with P 2 S 5 in the presence of Et3N in a 4:1:2 molar ratio in toluene under anhydrous conditions. These triethylammonium salts could be converted into sodium/ammonium salts, (o-, m-, or p-CH 3 C 6 H 4 O) 2 PS 2 Na/NH 4 , by their direct reaction with sodium metal in equimolar ratio or passing dry ammonia gas in toluene. These salts were characterized by elemental analyses (C, H, N, and S) and mass, IR, and NMR ( 1 H, 13 C, and 31 P) spectroscopic studies.

Preparation and structural organisation of heteroleptic tetraphenylantimony(V) complexes comprising unidentately and bidentately coordinated O, O′-dialkyldithiophosphate groups: Multinuclear ( 13C, 31P) CP/MAS NMR and single-crystal X-ray diffraction studies

O, O′-dipropyldithiophosphate and O, O′-di- iso-butyldithiophosphate (Dtph) tetraphenylantimony(V) complexes of the general formula [Sb(C 6H 5) 4{S 2P(OR) 2}] (R = C 3H 7, i-C 4H 9) were prepared and studied by means of 13C, 31P CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. Distorted octahedral and trigonal bipyramidal molecular structures have been established for prepared complexes. These unexpected structural distinctions between chemically related compounds are defined by the principally different coordination modes of O, O′-dipropyldithiophosphate and O, O′-di- iso-butyldithiophosphate ligands in their molecular structures (i.e., S, S′-bidentate chelating and S-unidentately coordinated, respectively). To characterise quantitatively phosphorus sites in both species of dithiophosphate ligands, 31P chemical shift anisotropy parameters ( δ aniso and η) were calculated from spinning sideband manifolds in MAS NMR spectra. The 31P chemical shift tensors for the bidentate chelating and unidentately coordinated dithiophosphate ligands display a profoundly rhombic and nearly axially symmetric characters, respectively.