Dithiophosphate Ligands Research Articles

Synthetic, spectroscopic, X-ray structural and antimicrobial studies of 1,3-dithia-2-stibacyclopentane derivatives of phosphorus based dithiolato ligands

Some mixed 1,3-dithia-2-stibacyclopentane derivatives with phosphorus based dithiolato ligands of the types SCH 2 CH 2 SS ¯ bS ( S ) POGO ¯ {where G = CH(Me) CH(Me) and C(Me) 2 C(Me) 2 } and SCH 2 CH 2 SS ¯ bS ( S ) P ( OR ) 2 {where R = Pr n , Bu n and Ph} have been synthesized by the reaction of 2-chloro-1,3-dithia-2-stibacyclopentane and the ammonium/sodium salt of the corresponding phosphorus based ligands in an equimolar ratio in anhydrous benzene solution. These yellow crystalline solid/semi-solid derivatives have been characterized by elemental analysis (C, H, S and Sb), molecular weights, melting point as well as spectral [UV, IR and NMR ( 1H, 13C and 31P)] studies. Single crystal X-ray diffraction analyses of 1,3-dithia-2-stibacyclopentane 2,3-butylenedithiophosphate revealed a monodentate mode of bonding of the dithiophosphate ligand in the complex. The free ligands and their antimony(III) complexes have also been screened for their antibacterial and antifungal activities.

Syntheses and molecular structures of ruthenium complexes with dithiophosphate ligands

Reactions of [Ru(PPh3)3Cl2] and [RuHCl(CO)(PPh3)3] with K[S2P(OEt)2] in THF afforded [Ru{S2P(OEt)2}2(PPh3)2] (1) and [RuH(CO){S2P(OEt)2}(PPh3)2] (2), respectively. The crystal structures of complexes 1 and 2 have been determined by X-ray crystallography. The ruthenium atom in both molecules of 1 and 2 adopt an octahedral configuration. The average Ru–P and Ru–S distances in 1 are 2.3324(10) and 2.4974(11) Å, respectively. The corresponding bond lengths for 2 are 2.3551(9) and 2.5474(11) Å.

Synthesis, spectroscopic characterization of O, O-alkylene dithiophosphates of tellurolane and 1-oxa-4-tellurane. Single crystal structures of C 4H 8Te[S 2P(OCH 2) 2CMe- nPr] 2 and C 4H 8OTe[S 2P(OCH 2) 2CEt 2] 2

The synthesis of the four disubstituted organotellurium (IV) compounds, C 4H 8Te[S 2P(OCH 2) 2CEt 2] 2 ( 1), C 4H 8Te[S 2P(OCH 2) 2CMe- n Pr] 2 ( 2), C 4H 8OTe[S 2P(OCH 2) 2CEt 2] 2 ( 3), C 4H 8OTe[S 2P(OCH 2) 2CMe- n Pr] 2 ( 4), and one monosubstituted compound C 4H 8OTe(I)[S 2P(OCH 2) 2CMe- n Pr] ( 5), was achieved. All compounds were characterized by IR, EI, MS, and multinuclear NMR ( 1H, 13C, 31P, 125Te). In addition, the molecular structures of 2 and 3 were determined by X-ray analyses. Both structures are monomeric and the tellurium atom is bonded to two carbon atoms and to one sulfur atom of each one of the two anisobidentate dithiophosphate ligands. In 2, the geometry around Te(IV) is as that of a sawhorse structure in which the lone pair is apparently stereochemically active and occupying an equatorial position in a ψ-trigonal bipyramid. However, when the second sulfur atom of the dithiophosphate ligand is included in the coordination sphere, the environment about tellurium in the compound 2 can be described as bicapped ψ-trigonal bipyramid. Whereas in 3 it is a distorted octahedral structure in which the lone pair is stereochemically inactive.

The unique alternation of conformationally different (‘chair’-‘saddle’) eight-membered metallocycles [Cd 2S 4P 2] in the chains of cadmium dialkyldithiophosphates: 13C, 31P, 113Cd CP/MAS NMR and single-crystal X-ray diffraction studies

O, O′-Dipropyldithiophosphate and O, O′-dibutyldithiophosphate (Dtph) cadmium(II) complexes were prepared and studied by means of heteronuclear 31P, 113Cd, 31C CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. Linear-chain polynuclear structures have been established for both cadmium(II) complexes, in which each pair of equivalent dithiophosphate groups, playing the same bridging structural function, asymmetrically links the neighbouring cadmium atoms. One remarkable structural feature of the synthesised cadmium(II) compounds is defined by the alternation of two types of conformationally different (‘chair’–‘saddle’) eight-membered rings [Cd 2S 4P 2] in the polymeric chains. Therefore, in both 31P NMR and XRD data, the bridging dithiophosphate ligands exhibit structural inequivalence in pairs. The structural states of both Dtph ligands and cadmium atoms have been characterised by the 31P and 113Cd chemical shift tensors, which display a profound axially symmetric and mainly rhombic characters, respectively. All experimental 31P resonances were assigned to the phosphorus structural sites in both resolved structures.

Synthesis and coordination chemistry of perfluoroalkylated dithiophosphate ligands

Dithiophosphoric acids [HS 2P(OC 2H 4C n F 2 n+1 ) 2] ( n = 4, 6) have been prepared in high yields. Deprotonation and reaction with transition metal substrates affords fluorous metal complexes which have been characterised by elemental analysis, mass spectrometry, IR and NMR spectroscopies. The structures of [Cu{S 2P(OC 2H 4C n F 2 n+1 ) 2}(PPh 3) 2] ( n = 4, 6) and [Cu{-S 2P(OC 2H 4C 4F 9) 2}(PPh 3)] 2 have been determined by single crystal X-ray diffraction.

Triphenylphosphine adducts of silver di-iso-propyl dithiophosphate

AbstractThe molecular structure of dimeric {[S2P(OiPr)2](PPh3)}2· 2 CHCl3is built up about a centrosymmetric eight-membered ring that adopts a chair conformation as a result of bidentate bridging dithiophos phate ligands. The silver atom is in a trigonal planar geometry. Relatively close transannular Ag…S interactions are noted which, if considered significant, leads to a tridentate dithiophosphate ligand and a distorted tetrahedral geometry for silver. The presence of two PPh3molecules in the coordination sphere of silver in monomeric Ag[S2P(OiPr)2](PPh3)2· 3 CHCl3as well as a bidentate di thiophosphate ligand gives rise to a tetrahedral geometry. Adducts with lower or greater numbers of PPh3ligands could not be obtained pointing to the inherent stability of the characterised structures.

Cluster self-assembly of centered cubes of copper(I) with dialkyldithiophosphate ligands. X-ray structures of [Cu8(DDP)6(μ8-X)]PF6 (DDP = S2P(OiPr)2; X = Cl or Br) and their relationship to oxide and sulfide centered zinc(II) dialkyldithiophosphates, [Zn4(DDP)6(μ4-S or O)

A high purity synthesis of chloride-{Cu8[S2P(OiPr)2]6(μ8-Cl)}[PF6] (1) and bromide-{Cu8[S2P(OiPr)2]6(μ8-Br)}[PF6] (2) centered Cu8 cubic clusters has been achieved through the reaction of [Cu(CH3CN)4]PF6 and NH4[S2P(OiPr)2] in the presence of [BzEt3N]X (X=Cl or Br) in THF upon addition of an appropriate oxidant. The nearly perfect Cu8 cube encapsulates the closed shell ions Cl− or Br−. The six diisopropyl dithiophosphate ligands bridge across each face of the Cu8 cube to form a nearly regular icosahedron of S atoms about the centered Cu8 cube. The eight Cu(I) atoms are located at the cube corners with an average Cu–Cu distance of 3.113(2) and 3.167(1) Å (1 and 2, respectively). The average Cu–S distance is 2.282(2) Å in 1 and 2.295(3) Å in 2. There appears to be a direct structural relationship between these centered cubal structures and the tetranuclear zinc(II) oxide and sulfide centered dialkyldithiophosphates, [Zn4(DDP)6(μ4-S or O)] which have the classic “basic” beryllium acetate geometry. The structural relationship to the hexanuclear clusters Cu6[S2P(OR)2]6, R=ethyl or n-butyl, also are described.

Syntheses and structures of silver(I) clusters uniquely exhibiting three distinct binding modes, two of which are novel, for a dithiophosphate ligand

An unprecedented, triply bridging sulfur atom of the dithiophosphate ligand was observed in the new silver cluster cation, Ag4(μ-dppm)2[S2P(OEt)2]3+, where the coordination geometry for the trifurcated sulfur atom exhibited distorted seesaw.

Alkyl Transfer Reactivity in the First Octahedral Isocyanide Complex of Nickel(II)

[Ni{S2P(OEt)2}2] (1) reacts with 2 equiv of CNXyl (Xyl = 2,6-dimethylphenyl) to afford [Ni{S2P(OEt)2}2(CNXyl)2] (2), which, as confirmed by X-ray crystallography, is the first octahedral isocyanide complex of Ni(II). Reaction of 2 with PCy3 (2 equiv) produces square-planar [Ni{S2P(O)(OEt)}(PCy3)(CNXyl)] (3). When 2 is reacted with only 1 equiv of PCy3, the final product is the square-planar complex [Ni{S2P(O)(OEt)}(CNXyl)2] (4), containing two isocyanide ligands. Compound 4 reacts with 2-fold excess PCy3 to give 3 via isocyanide displacement. Both 3 and 4 contain one ethyldithiophosphate ligand, which is produced by the transfer of one ethyl group from a coordinated diethyl dithiophosphate of complex 2 to the leaving diethyl dithiophosphate ligand. Experimental evidence indicates that the phosphine plays a significant role in the alkyl transfer. Moreover, reaction of 1 with 2 equiv of N-p-tolyl-2-iminopyridine affords octahedral [Ni{S2P(OEt)2}{2-pyCHNC6H4-Me-4}2][S2P(OEt)2] (5), in which both free and coordinated diethyl dithiophosphate coexist without any transfer of alkyl.

Complexation of lead(II) with O, O′-dialkyldithiophosphate ligands: 31P and 13C CP/MAS NMR and single-crystal X-ray diffraction studies

Polycrystalline lead(II) complexes with O, O ′-dipropyl- and O, O ′-di- cyclo-hexyldithiophosphate ions were prepared and studied by means of 31P, 31C CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. Prepared complexes are characterised by polynuclear structures, in which pairs of dithiophosphate groups asymmetrically link neighbouring lead atoms, forming infinite linear zigzag chains. In spite of the same combined structural function, dithiophosphate ligands in both complexes display structural inequivalence. To characterise the combined structural state of the dialkyldithiophosphate ligands, 31P chemical shift anisotropy parameters, δ aniso and η, were estimated from spinning sideband patterns in experimental CP/MAS NMR spectra for each of the two prepared complexes as well as the initial potassium O, O ′-dipropyl- and O, O ′-di- cyclo-hexyldithiophosphate salts.

Transfer of chirality by dithiophosphate ligands and chiral discrimination in the stereoselective formation of square-planar Ni(II) complexes.

In the formation reaction of Ni(2+) with the chiral racemic ligand, (R)(R)bdtp(-)/(S)(S)bdtp(-), bdtp(-) = [SSPOCH)CH(3))CH(CH(3))O](-), cyclo- O,O'-[1,2-dimethylethylene] dithiophosphato ion, the meso-complex Ni[(R)(R)(lambda)bdtp][(S)(S)(delta)-bdtp] is stereoselectively produced. The meso-complex was compared with the enantiopure crystals of (+)(589)Ni[(R)(R)(lambda)bdtp](2) or (-)(589)Ni[(S)(S)(delta)bdtp](2), as well as racemic crystals, rac-(+/-)Ni[bdtp](2), which were prepared from the solution containing the two enantiomers in a 1:1 ratio. Dissociation constants in solutions indicate different stability of the meso and enantiopure complexes depending on the solvent, whereas a more efficient crystal packing, weak H-bonding, and nonbonding interactions contribute to stabilization of the meso-species over the racemic one. Molecular structures show that the outer five-membered ligand ring adopts the half-chair conformation C(2) with either the lambda or the delta chirality and the methyl groups are in equatorial (e) positions. Enantiopure ligands of (+)(589)Ni[(R)(R)(lambda)bdtp](2) and (-)(589)Ni[(S)(S)(delta)bdtp](2) induce chirality into the symmetric SSNiSS chromophore with slightly helical distortion. Thus, their CD spectra exhibit weak negative or positive Cotton effects at 662 nm. CD spectra in L(+)- and D(-)diethyltartrate of the meso-complex and racemic crystal, rac-(+/-)Ni[bdtp](2), exhibit different weak Cotton effects of opposite sign. Complexes dissociate in methanol; rac-(+/-)Ni[bdtp](2) in methanol undergoes a crystallization-induced second-order asymmetric transformation which finally yields crystals of the meso-Ni[(R)(R)(lambda)bdtp][(S)(S)(delta)bdtp] complex.

Crystal structures and nonlinear optical properties of new clusters [MOS 3Cu 3(PPh 3) 3{S 2P(OCH 2Ph) 2}] (M=Mo, W)

Two new isostructural O, O′-dialkyl dithiophosphate-containing sulfido clusters, MOS 3Cu 3(PPh 3) 3{S 2P(OCH 2Ph) 2}] (M=Mo ( 1); M=W ( 2)), were synthesized through reaction of [NH 4[MOS 3] with [CuS 2P(OCH 2Ph) 2]. They possess an incomplete cubane-like structure, in which the dithiophosphate ligand adopts a triply bridging role, employing one sulfur atom to bind to one Cu atom and the other to two Cu atoms. High third-order nonlinear optical properties of the two clusters were observed, and Z-scan data measured with 532 nm nanosecond laser pulses showed effective third-order optical nonlinearities α 2=0.78×10 −10 and 1.16×10 −10 m W −1, and n 2=−7.8×10 −18 and 4.0×10 −18 m 2 W −1, respectively, for DMF solution of compound 1 and DMF solution of 2. These two clusters exhibit large optical limiting performance with limiting threshold values of 220 mJ cm −2 for 1 and 600 mJ cm −2 for 2.

Polycrystalline and surface O, O′-dialkyldithiophosphate zinc(II) complexes: preparation, 31P CP/MAS NMR and single-crystal X-ray diffraction studies

Dithiophosphate zinc(II) complexes with eight different O, O′-dialkyldithiophosphate ligands have been prepared in solid/liquid states and as surface complexes on a synthetic sphalerite, and studied by means of 31P NMR spectroscopy. All 31P resonances, corresponding to dithiophosphate ligands with different structural functions (i.e. terminal chelating or bridging between two metal atoms in bi- and tetranuclear complexes), have been assigned on the basis of comparative analyses of chemical shift data for solid complexes, their melts and chloroform solutions at various concentrations. The bridging coordination of O, O′-dialkyldithiophosphate ligands by the two neighbouring zinc(II) atoms was established in the case of zinc(II) complexes formed at the surface of the synthetic sphalerite. In addition, novel molecular and crystal structures of the binuclear O, O′-di- cyclo-hexyldithiophosphate zinc(II) complex have been resolved by single-crystal X-ray diffraction data analysis, and useful correlations with 31P NMR data for this complex were obtained.

Optically-active tris( O, O′-dialkyl dithiophosphato- S, S′)chromium(III) complexes. Isolation of diastereoisomers and isomerization reactions

Two optically-active O, O′-dialkyl dithiophosphate ligands, (Bor) 2PS 2 − and (Men) 2PS 2 − , were prepared from P 2S 5 and the monoterpene alcohols, d-borneol and l-menthol. The chromium(III) complexes, [Cr{(Bor) 2PS 2} 3] and [Cr{(Men) 2PS 2} 3], were prepared by reaction with Cr(NO 3) 3·9H 2O in acetone. The diastereoisomers (Δ and Λ) were separated by fractional crystallization of the complexes from toluene ([Cr{(Bor) 2PS 2} 3]) or acetone ([Cr{(Men) 2PS 2} 3]). The (−) 680 CD -Δ-[Cr{(Bor) 2PS 2} 3] isomer was obtained from the less soluble part. This isomer shows extremely strong CD, Δ ε (680 nm, toluene)=−15.0 M −1 cm −1. The Δ-[Cr{(Men) 2PS 2} 3] isomer could not be obtained in the optically-pure state, since the complex inverts appreciably during the recrystallization procedure. Activation parameters for isomerization (epimerization), Δ→Λ and Λ→Δ were determined for both complexes, [Cr{(Bor) 2PS 2} 3] and [Cr{(Men) 2PS 2} 3]. [Cr{(Men) 2PS 2} 3] isomerizes much faster than [Cr{(Bor) 2PS 2} 3].

Synthesis, characterization and X-ray structure of stannocanes substituted with a cyclic dithiophosphate ligand X(CH 2CH 2S) 2Sn nBu [S 2P(OCH 2C(Et 2)CH 2O)], (X=O, S): a study about the conformational tendencies and the relationship with the anomeric effect of the stannocane rings

The preparation and conformational study of two stannocanes, 5- n-butyl-5-(5′,5′-diethyl-2′-thioxo-1′,3′,2′-dioxaphosphorinane-2′-thiolate)-1-oxa-4,6-dithia-5-stannocane, O(CH 2CH 2S) 2Sn n Bu[S 2P(OCH 2CEt 2CH 2O)] ( 1) and 2- n-butyl-5-(5′5′-diethyl-2′-thioxo-1′,3′,2′-dioxaphosphorinane-2-thiolate)-1,3,6-trithia-2-stannocane S(CH 2CH 2S) 2Sn n Bu[S 2P(OCH 2CEt 2CH 2O)] ( 2) is reported. These compounds were prepared from the corresponding chloro-oxa and -thia-stannocanes and the sodium salt of dithiophosphoric acid (2-mercapto-2-thiono-1,3,2-dioxaphosphorinane) in ethanol. Compounds 1 and 2 were characterized by IR, EI-MS and multinuclear NMR ( 1H, 13C, 31P). The molecular structures were determined by X-ray analyses. The eight-membered ring in both compounds has a boat–chair conformation with a 1,5 transannular Sn⋯O (2.468 Å), Sn⋯S (2.94 Å) interaction. The 1,3,2-dioxaphosphorinane ring in 1 and 2 present a chair conformation with the stannocane in the axial position, in accordance with the anomeric effect. The coordination of the Sn-atoms is trigonal-bipyramidal in 1 and intermediate between trigonal-bipyramidal and a bicapped tetrahedral arrangement in 2.

Synthesis, crystal structure and nonlinear optical properties of two new cluster compounds: [WCu 3S 4(PPh 3) 3{S 2P(OCH 2Ph) 2}] and [WAg 3OS 3(Ph 3P) 3{S 2P(OPr i) 2}

Two new O, O′-dialkyl dithiophosphate-containing sulfido clusters, [WCu 3S 4(PPh 3) 3{S 2P(OCH 2Ph) 2}] 1 and [WAg 3OS 3(Ph 3P) 3{S 2P(OPr i) 2}] 2, were synthesized through reactions of [NH 4] 2[WS 4] with [CuS 2P(OCH 2Ph) 2] and [NH 4] 2[WOS 3] with [AgS 2P(OPr i) 2], respectively. Their crystal structures and nonlinear optical properties are reported. The X-ray crystallographic structure of 1 is an incomplete cubane-like structure, the dithiophosphate ligand adopts a triply bridging role, employing two sulfur atoms to coordinate to the three Cu atoms: one sulfur atom binds to one Cu atom, another sulfur atom to two other Cu atoms. The structure of 2 contains a half-open cubane-like cluster core, the dithiophosphate ligand acts as a bidentate ligand and the two S atoms of the di-isopropyl dithiophosphato ligand coordinate to two Ag atoms, respectively. Using a Z-scan technique with 532 nm laser radiation, both the real and imaginary parts of third-order nonlinear susceptibility of clusters 1 and 2 were determined.

Chloro(diethyl dithiophosphato-S,S')(triphenylphosphine-P)palladium(II)

The structure of the title compound, [PdCl(C 4 H 10 O 2 PS 2 )(C 18 H 15 P)], is reported. There are two independent molecules in the asymmetric unit. The coordination around the Pd atom in each molecule is distorted square planar. Both molecules have nearly the same conformation, except for the orientation of the ethyl groups on the dithiophosphate ligand. Bond lengths and angles are typical of related Pd and Pt complexes.

Activation of Ligand Reactivity: Thiolate C-S and Dithiophosphate Ester C-O Heterolyses within a Dimolybdenum(V) System.

Ligand reactivity was demonstrated for sulfide alkylation, thiolate dealkylation, and dithiophosphate de-esterification within molybdenum(V) dimers. The cationic complex [Mo(2)(NC(6)H(4)Me)(2)(S(2)P(OEt)(2))(2)(&mgr;-O(2)CMe)(&mgr;-SR)(2)](+) was inductively activated toward thiolate C-S and dithiophosphate C-O heterolyses. The dealkylations were studied using anionic nucleophiles, and various reactivity patterns were characterized. The de-esterification of the diethyl dithiophosphate ligands produced complexes containing the rare monoester EtO(O)PS(2)(2)(-) ligand. This ligand's phosphoryl group was poorly nucleophilic but weakly basic. Crystallographic comparisons between the activated cation and the neutral complex [Mo(2)(NC(6)H(4)Me)(2)(S(2)P(OEt)(2))(2)(&mgr;-O(2)CMe)(&mgr;-S)(&mgr;-SMe)] were conducted to delineate structural differences related to the activation. A crystallographic study was also done of the complex [Mo(2)(NC(6)H(4)CH(3))(2)(S(2)P(OEt)(2))(S(2)P(O)OEt)(&mgr;-O(2)CMe)(&mgr;-SEt)(2)], which provided internal comparison of monoester EtO(O)PS(2)(2)(-) and diester (EtO)(2)PS(2)(-) ligand types.

A Trinuclear Molybdenum Cluster Coordinated byo-Nitrobenzoate

The title compound, tris(diethyl dithiophosphato)-1κ 2 S,S';2κ 2 S,S'; 3κ 2 S,S'-μ-o-nitrobenzoato-2κO:3κO'-pyridine-1κN-μ 3 -thio-tri-μ-thio-1:2κ 2 S,1:5κ 2 S,2:3κ 2 S-triangulo-trimolybdenum(3 Mo-Mo), [Mo 3 S 4 (C 7 H 4 N(C 4 H 10 PS 2 ) 3 (C 5 H 5 N)], was synthesized in a mixed solvent of acetonitrile and ethanol by a ligand substitution reaction in which o-nitrobenzoic acid replaces the bridging diethyl dithiophosphate (DTP) ligand. The average Mo-Mo bond distance is 2.731 (2) A. The substitution of o-nitrobenzoate for DTP shortens the Mo-Mo bond that it bridges to 2.693 (1) A.

Dicarbonyl dithio ligand complexes of tungsten(II)

Reaction of LWI(CO) n [L=hydrotris(3,5-dimethylpyrazol-1-yl)borate, n=2, 3] with NH 4[S 2PR 2] [R=OEt, OPr i , (−)-mentholate (R*), Ph] in acetonitrile or THF results in the formation of the dithio ligand complexes LW(S 2PR 2- S)(CO) 2. The yellow–orange, diamagnetic complexes exhibit IR spectra featuring two ν(CO) bands at ca. 1950 and 1840 cm −1 and 1H-NMR spectra consistent with fluxional behavior in solution. Crystallographic characterisation of LW{S 2P(OPr i ) 2- S}(CO) 2 revealed a six-coordinate, distorted octahedral complex composed of a tungsten center coordinated by a monodentate dithiophosphate ligand, two cis carbonyl ligands, and a facial, tridentate L ligand. Unlike analogous complexes bearing strictly monodentate sulfur donor ligands, the LW(S 2PR 2)(CO) 2 complexes undergo reactions with oxygen atom donors to produce (carbonyl)oxo complexes of the type LWO(S 2PR 2- S)(CO).