Adducts of mononuclear oxomolybdenum(IV)O,O′-dialkyl(alkylene) dithiophosphate complexes with pyridine, 2,2′-bipyridyl and 1, 10-phenanthroline

Summary Equimolar adducts of mononuclear oxomolybdenum(IV)O,O-dialkyl and alkylene dithiophosphates with heterocyclic amines, MoO[S₂P(OR)₂]₂·L (where when R=Et,i-Bu; L=pyridine and when R=Et,n-Pr,i-Bu; L=2,2-bipyridyl, 1,10-phenanthroline) and (where G=CH₂CMe₂CH₂, L=2,2-bipyridyl and when G=CMe₂CMe₂; L=pyridine) have been prepared by reacting the corresponding oxomolybdenum(IV) complexes with an excess of pyridine or with bipyridyl or phenanthroline in a 11 molar ratio.The complexes have been characterized by elemental analyses and molecular weight determinations. Their probable structures are proposed on the basis of i.r. and n.m.r. (¹H,¹³C and³¹P) spectral data, which are consistent with a 6-coordinated octahedral structure for all the base adduct complexes.     

Synthesis,spectral characterization,and evaluation of antimicrobial activity of O,O′-alkanediyl S-(N-phthalimidomethyl) dithiophosphates and zinc bis(O,O′-alkanediyl) dithiophosphates

The synthesis of novel dithiophosphate derivatives has been achieved. Two O,O′-alkanediyl S-(N-phthalimidomethyl) dithiophosphates and two Zinc bis(O,O′-alkanediyl) dithiophosphates are synthesized by an easy and facile chemical synthetic route. Zinc bis[O,O′-(2-methylpentane-2,4-diyl) dithiophosphate] L¹, Zinc bis[O,O′-(2-ethylhexane-1,3-diyl) dithiophosphate] L², O,O′-(2-methylpentane-2,4-diyl) S-(N-phthalimidomethyl) dithiophosphate L³ and O,O′-(2-ethylhexane-1,3-diyl) S-(N-phthalimidomethyl) dithiophosphate L⁴ are synthesized from the respective ammonium salts. Compounds L¹, L², L³, and L⁴ are characterized by (CHN) elemental analysis, ESI mass, FT-IR, ¹H, ¹³C, and ³¹P NMR techniques. The crystal structure of ammonium O,O′-(2-methylpentane-2,4-diyl) dithiophosphate is discussed. L¹, L², L³, and L⁴ were evaluated for antimicrobial activity. It was found that the phthalimide derivatives L³ and L⁴ showed much better antifungal potential against some species of fungus. The Zinc dithiophosphates L¹ and L² showed good antibacterial activity against Bacillus cereus and Escherichia coli.     

Triisopropoxyniobium(V) and tantalum(V)bis-O,O′-dialkyl dithiophosphates

Summary Triisopropoxy bis(O,O-dialkyl dithiophosphates), (i-PrO)₃M[S₂P(OR)₂]₂ (M = Nb^v, Ta^v; R = n-Pr, i-Pr, i-Bu and Ph) have been prepared by reacting the appropriate triisopropoxymetal(V)dichloride, (i-PrO)₃MCl₂ (1 mol) with sodium/ammonium dialkyl dithiophosphates (2 mols)in THF. The monomeric products which are viscous liquids, soluble in common organic solvents and highly susceptible to hydrolysis, were characterized by i.r. and n.m.r. spectra which indicate a bidentate mode of attachment of dithiophosphato groups to the metal.     

Synthesis and characterization of nitrogen-containing Lewis base adducts of bis(O,O′-dialkylmonoselenophosphato)cobalt(II) complexes

The adducts of bis(O,O′-dialkylmonoselenophosphato)cobalt(II) complexes, Co{O(Se)P(OR)₂}₂(L)₄ (where R?=?n-Pr, i-Pr; L?=?C₅H₅N, NC₅H₄Me-2, NC₅H₄Me-3), were synthesized by in situ reactions of CoCl₂?·?6H₂O, Lewis base, and NaO(Se)P(OR)₂. The single crystal structure of Co{O(Se)P(OⁱPr)₂}₂(C₅H₅N)₄ shows distorted octahedral geometry around cobalt(II) and monoselenophosphates are trans. The CoN₄ forms a square plane. These bis(O,O′-dialkylmonoselenophosphato)cobalt(II) adducts were characterized by elemental analyses, spectroscopic techniques (UV-Vis, infrared, ¹H and ³¹P), and magnetic moment measurements.     

Preparation and characterization of tetrakis (β-ketophosphonato) thorium(IV) complexes

Tetrakis (β-ketosphonato) thorium(IV) complexes have been prepared using a liquid—liquid extraction method. They have been well characterized by i.r., Raman, ¹H, ¹³C and ³¹P NMR spectroscopies. β-ketophosphonates act as anionic chelating ligands and are coordinated by the PO and CO oxygen atoms. An asymmetric repartition of the negative charge on the chelate ring is observed. A stabilities order of the studied β-ketophosphonato-thorium complexes has been established.     

Synthesis and structural characterization of iron–sulfur complexes with hydrophilic nitrogen–phosphorus ligands

Reaction of the parent complex (μ-PDT)Fe₂-(CO)₆ (A) (PDT = 1,3-SCH₂CH₂CH₂S^2?) with the bidentate N/P ligand [(Ph₂P)₂N(C₆H₄Cl-p)] in the presence of Me₃NO as decarbonylating agent produced an unexpected iron–sulfur complex [(μ-PDT)Fe₂(CO)₅{PPh₂(NHC₆H₄Cl-1,4)}] (1). Extending this chemistry further, two similar complexes [(μ-PDT)Fe₂(CO)₅{PPh₂(NHC₆H₄NO₂-1,4)}] (2) and [(μ-PDT)Fe₂(CO)₅{PPh₂(NHC₆H₄CO₂Et-1,4)}] (3) could be prepared from the simple substitution reactions of the precursor A with the monodentate N/P ligands Ph₂P(NHC₆H₄NO₂-1,4) and Ph₂P(NHC₆H₄CO₂Et-1,4), respectively. These new complexes, which can be considered as active site models of [FeFe] hydrogenases, have been characterized by elemental analysis, FTIR, and NMR (¹H, ¹³C, ³¹P) spectroscopies, as well as by X-ray crystallography for complex 1.     

Synthesis,spectral characterization and antibacterial activity of O,O’-dialkyl and alkylene dithiophosphatogold (III)dichloride; crystal structure of [S2POCMe2CMe2O]AuCl2

Abstract

O, O’-Dialkyl and alkylene dithiophosphatogold (III)dichloride complexes of the type [(RO)₂PS₂]AuCl₂ and [S₂POGO]AuCl₂, where R?=?Et, nPr, iPr, iBu, Ph, cyclohexyl and cyclopentyl, where G?=?CMe₂CMe₂-, have been synthesized in 80-90% yields by reaction of the corresponding acid or sodium salts of the appropriate dithiophosphoric acids in 1:1 ratio with gold (III) chloride in dry dichloromethane at room temperature. The compounds have been characterized by elemental analyses, IR and (¹H, ^l3C, and ³¹P) NMR. The crystal structure of [S₂POCMe₂CMe₂O]AuCl₂, was determined. These new complexes have shown their growth inhibiting potential against various bacterial strains with moderate to good activity.     

Trichloro- and triisopropoxy-niobium(V) and tantalum(V) bis -( O,O ′-alkylene dithiophosphates): synthesis and characterization

Trichloro- and triisopropoxy-niobium(V) and tantalum(V) alkylene dithiophosphates, (M = Nb(V) or Ta(V); G =–CHMeCHMe–,–CMe₂CMe₂–,–CH₂CMe₂CH₂–,–CH₂CEt₂CH₂–or–CMe₂CH₂CHMe–and X = Cl or OPrⁱ) have been synthesized by reaction of metal(V) chloride, MCl₅, or triisopropoxymetal(V) dichloride, (PrⁱO)₃MCl₂, with the sodium salts of O,O′-alkylene dithiophosphoric acids, in 1 : 2 molar ratio in THF under anhydrous conditions. These pink-purple or light-yellow compounds are viscous, semi-solid or solid, hydrolyzable and soluble in common organic solvents. These compounds have been characterized by elemental analyses, molecular weight determinations and spectral studies like IR and heteronuclear NMR (¹H, ¹³C and ³¹P), which indicated a bidentate mode of chelation of dithio ligands, leading to a pentagonal bipyramidal geometry around the niobium(V) or tantalum(V) centers.     

Preparation and characterization of octacyanomolybdates(IV and V) and octacyanotungstates(IV and V) with 2,2′-bipyridylium cation

Reaction of protonated 2,2′-bipyridine (bpy) with octacyanometalates(IV and V), [M(CN)₈]ⁿ⁻ (M = Mo or W, n = 3 or 4), gave the following complexes: {(bpyH)₃[M(CN)₈]·4H₂O}, {(bpyH)₃(H₃O)[M(CN)₈]·H₂O}, {(bpyH₂)₂[W(CN)₈]·3H₂O} and {(bpyH₂)K₂[W(CN)₈]·2H₂SO₄·7H₂O}. These salts were characterized by electron absorption and reflectance spectrometry, IR, Raman and ESR spectrometry, thermo gravimetry and differential thermal analysis, cyclic voltammetry and potentiometry. The solubility of the salts in water and some polar organic solvents has been measured. The intensively coloured salts of molybdenum(IV) and tungsten(IV) have been discussed in terms of the bpyH⁺-[M(CN)₈]⁴⁻ ion pairs, which exhibit an outer-sphere electron transfer between adjacent redox sites.     

Synthesis and Characterization of O,O′ Dialkyl and Alkylene Dithiophosphates of Lanthanum(III) and their Adducts with Nitrogen and Phosphorus Donor Bases

Lanthanum(III) tris(dithiophosphates), [La{S₂P(OR)₂}₃] (where R=-CH₂CH₂CH₃ or -C₆H₅) and [La{S₂PO₂G}₃] [where G=-C(CH₃)₂CH₂CH(CH₃)-, -CH₂C(CH₃)₂CH_2-, -C(CH₃)₂C(CH₃)_2- and -CH₂CH₂CH(CH₃)-] were prepared in methanolic solutions of anhydrous LaCl₃ and ammonium dithiophosphates. Addition complexes of the type [La{S₂P(OR)₂}₃·nL] and [La{S₂PO₂G}₃·nL] [where n = 1, L = N₂C₁₀H₈ or N₂C₁₂H₈ and n = 2, L = P(C₆H₅)₃] were prepared by reaction of lanthanum(III) tris(dithiophosphates) and nitrogen or phosphorus donor bases in benzene. These newly synthesized derivatives have been characterized by elemental analyses, molecular weights, IR, ¹H and ³¹P NMR spectral measurements. Coordination numbers of six and eight are suggested for lanthanum(III) in these derivatives.     

Synthesis and characterization of adducts of p-azidostyrene derivatives to fullerene C_(60)

Fullerene C60 reacted with p-azidostyrene derivatives in refluxing chlorobenzene,yielding monoadducts 2a and 2d as well as diadduct 2c with aziridine structure at 6/6-ring junctions.Experimental results showed that the addition of the second azide to the monoadduct was regioselective.The diadduct,of Cs symmetry in C60 moiety,was unstable by opening to be 1,6-imido[10]annulene structure.     

Synthesis,characterization, and cytotoxicity of Pt(IV) complexes containing 1,10-phenanthroline and 2,2′-bipyridine and diaminocyclohexane ligands

Four platinum(IV) complexes containing intercalating ligands [1,10-phenanthroline (phen) and 2,2′-bipyridine (bpy)] and ancillary ligands [(1S,2S)-diaminocyclohexane (SS-DACH) and (1R,2R)-diaminocyclohexane (RR-DACH)] were synthesized and characterized by ¹H nuclear magnetic resonance, electrospray ionization mass spectrometry, X-ray crystal structure analysis, elemental analysis, ultraviolet absorption spectroscopy, circular dichroism spectroscopy, and electrochemical analysis. The reactions between [Pt(phen)(SS-DACH)Cl₂]²⁺ and glutathione and Ac-CPFC-NH₂ were investigated by high-performance liquid chromatography. [Pt(phen)(SS-DACH)Cl₂]²⁺ was reduced to its corresponding Pt(II) complex [Pt(phen)(SS-DACH)]²⁺, while glutathione and Ac-CPFC-NH₂ were oxidized to glutathione-disulfide and a peptide containing an intramolecular disulfide bond, respectively. The cytotoxicities of the Pt(IV) complexes against a human non-small cell lung cancer cell line (A549) and the corresponding cisplatin-resistant cell line (A549cisR) were evaluated. These Pt(IV) complexes showed a higher activity toward A549 and A549cisR than did cisplatin. Also, the cytotoxicities of the Pt(IV) complexes were higher for A549cisR than for A549 cells. Moreover, the cytotoxicities of the (SS-DACH)-liganded platinum complexes were higher than those of the (RR-DACH)-liganded platinum complexes in either A549 or A549cisR cells. Phen-liganded platinum complexes were more cytotoxic than the bpy-liganded platinum complexes. The cytotoxicities of these Pt(IV) complexes had no correlation with reduction potentials.     

Synthesis and characterization of lead(II) complexes with substituted 2,2′-bipyridines,trifluoroacetate, and furoyltrifluoroacetonate

Two substituted 2,2′-bipyridine lead(II) complexes, [Pb(5,5′-dm-2,2′-bpy)(tfac)₂] _n (1) (5,5′-dm-2,2′-bpy?=?5,5′-dimethyl-2,2′-bipyridine and tfac?=?trifluoroacetate) and [Pb₂(4,4′-dmo-2,2′-bpy)₂(ftfa)₄] (2) (4,4′-dmo-2,2′-bpy?=?4,4′-dimethoxy-2,2′-bipyridine and ftfa?=?furoyltrifluoroacetonate), have been synthesized and characterized by elemental analysis, IR, ¹H NMR, and ¹³C NMR spectroscopies, thermal behavior, and X-ray crystallography. Complexes 1 and 2 are 1D coordination polymer and dinuclear complex, respectively. The supramolecular features in these complexes are guided by weak directional intermolecular interactions.     

Synthesis,characterization, and interaction with DNA of Cu(II) and Zn(II) complexes with 2,2′-bipyridyl-6,6′-dicarboxylic acid

Two transition metal complexes, [Cu₂(bpdc)₂H₂O]·2H₂O (1) and Zn(bpdc)(H₂O)₂ (2) (H₂bpdc?=?2,2′-bipyridine-6,6′-dicarboxylic acid), were synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Complex 1 is dinuclear with two five-coordinate cupric ions and 2 is mononuclear with one six-coordinate zinc. Interactions of 1 and 2 with DNA have been investigated using UV–Vis absorption spectra. The cleavage reaction on DNA has been monitored by agarose gel electrophoresis.     

Synthesis,characterization, and cytotoxicity of complexes of platinum(II) with 2,2′-bipyridine and N-benzoyl-L-amino acid dianion

Four new platinum(II) complexes (1–4) with N-benzoyl-L-amino acid and bipy were synthesized and characterized by elemental analysis, IR, UV, ¹H NMR, and mass spectra. The crystal structure of 1 was determined by X-ray diffraction analysis. Cytotoxicities were measured by MTT and SRB assays. Complexes 1–4 exert cytotoxicity with selectivity against HL-60, Bel-7402, BGC-823, and KB cell lines. This suggests that amino acids and acylated groups have important effects on cytotoxicity; the cytotoxicity is also related to the species of tumor cells, but the IC₅₀ values do not show definite correlation with the variation of amino acids and acylated groups.     

Synthesis and characterization of N,N,N′,N′-tetraalkyl-4-oxaheptanediamide as extractant for extraction of uranium(VI) and thorium(IV) ions from nitric acid solution

Tridentate ligand N,N,N′,N′-tetraoctyl-4-oxaheptanediamide(TOOHA) and other three analogous diamides have been prepared and characterized by using NMR spectra and element analysis. The extraction of UO₂ ²⁺ and Th⁴⁺ with the present extractants was investigated at 293 ± 1 K from nitric acid solutions. n-Octane was found to be the most suitable diluent in the present study compared with other diluents tested. Extraction distribution ratios (D) of U(VI) and Th(IV) have been studied as a function of aqueous concentrations of HNO₃, extractant concentrations. The results indicated that U(VI) is mainly extracted as UO₂(NO₃)₂·2TOOHA. In the case of Th⁴⁺ ion, the possible compositions of extracted species in organic phase were presumed to be Th(NO₃)₄·2TOOHA and Th(NO₃)₄·3TOOHA. In addition, the influence of concentration of sodium nitrate as salting-out agent on the distribution ratio of U(VI) and Th(IV) with TOOHA was also evaluated.     

Synthesis and Characterization of Chlorobis(cyclopentadienyl) Titanium(IV) and Zirconium(IV) O,O’-Dialkyl and Alkylene Dithiophosphates

Abstract

Reactions of O,O′-dialkyl and alkylene dithiophosphoric acids with bis (cyclopentadienyl) titanium(IV) and zirconium (IV) dichloride in a 1:1 molar ratio in refluxing benzene proceeds with elimination of HCl and formation of the substituted derivatives, Cp₂MCl[S₂P(OR)₂] (where R = Et, Pr-n, Pr-i, Bu-i and Ph), Cp₂MCl[S₂POGO] (where G = ?CH₂CMe₂CH₂?, ?CH₂CEt₂CH₂? and ?CMe₂CMe₂?), (M = Ti and Zr). The complexes are dark red and yellow solids, soluble in common organic solvents and monomeric in nature. These have been characterized on the basis of elemental analyses, molecular weight determinations, IR, and NMR (¹H, ¹³C, and ³¹P).

GRAPHICAL ABSTRACT      

Nitrogen-donor base adducts of bis(O,O′-di-isoamyldithiophosphato)nickel(II)

A series of Ni^II complexes with the O,O-di-isoamylester of dithiophosphoric acid and nitrogen-donor ligands of composition [Ni(i-Am₂dtp)₂(L)]; [dtp = O₂PS₂ ^–; L = 2,2-bipyridine (bpy); 1,10-phenanthroline (phen); 5-nitro-1,10-phenanthroline (nphen); 4,7-diphenyl-1,10-phenanthroline (baphen); 2,9-dimethyl-1,10-phenanthroline (neo), 2-aminomethylpyridine (amp), 2-(2-aminoethyl)pyridine (aep), 2,2-dipiridylamine (dpa), 1,2-diaminopropane (1,2-dap) or trans 1,2-diaminocyclohexane (dch)] have been prepared. The compounds have been characterized by elemental analyses (C,H,N,S), electronic and i.r. spectroscopy, magnetic and conductivity measurements and by cyclic voltammetry. The results show that all complexes behave as non-electrolytes in acetone. Electronic spectra and magnetic moments suggest a distorted cis-octahedral geometry around the Ni^II atom [_eff/_B <3.10, 3.40 >], except for [Ni(i-Am₂dtp)₂(aep)], where the measured temperature dependence of the magnetic susceptibility proved the tetrahedrally coordinated nickel [4.06 _eff/_B (298 K) – 3.20 _eff/_B (80 K)]. In the [Ni(i-Am₂dtp)₂(neo)] complex, the nickel atom is penta-coordinated. The X-ray crystal and molecular structure of [Ni(i-Am₂dtp)₂(1,2-dap)] has been determined.