1,3-Diphosphapropenes for novel chemistry of metal complexes

2-Methyl-3,3-diphenyl-1-(2,4,6-tri-t-butylphenyl)-1,3-diphosphapropene was obtained as a chelate ligand for palladium(II) and platinum(II) complexes. Sulfurization of 2-methyl-1,3-diphosphapropene mainly gave 3-thioxo-1,3-diphosphapropene which bears a PC-PS skeleton and was used as a ligand of transition-metal complexes. A doubly-sulfurized product of the 1,3-diphosphapropene, 1,3-dithioxo-1,3-diphosphapropene, was isolated and characterized. The palladium(II) complexes containing the ligated 1,3-diphosphapropenes were used for catalytic reactions such as cross-couplings and direct conversion of allyl alcohol to allylaniline.     

Preparation,structure, and some coordination properties of 2-chloro-3,3-diphenyl-3-thioxo-1-(2,4,6-tri-t-butylphenyl)-1,3-diphosphapropene

A sterically encumbered 3-thioxo-1,3-diphosphapropene, bearing a P=C-P=S skeleton, was prepared, characterised, and allowed to react with a carbonyltungsten(0) reagent and iodine affording the corresponding chelate tungsten(0) complex and charge-transfer complex with iodine, respectively, which were analysed by the X-ray crystallography.     

Preparation and coordination properties including catalytic activities of a bulky 2-methyl-3-thioxo-1,3-diphosphapropene

[reaction: see text] 2-Methyl-3,3-diphenyl-3-thioxo-1-(2,4,6-tri-tert-butylphenyl)-1,3-diphosphapropene, which bears a P=C-P=S skeleton, was prepared and used as a ligand of transition-metal complexes. The palladium complexes containing the ligated 3-thioxo-1,3-diphophapropene were stable and used for catalytic reactions such as cross-couplings and direct conversion of allyl alcohol to allylaniline.     

Coordination Chemistry of a Bulky 1,3-Diphosphapropene with Carbonyltungsten(0) Moieties

( Z )-2-Chloro-3,3-diphenyl-1-(2,4,6-tri- t -butylphenyl)-1,3-diphosphapropene was derived from chlorodiphenylphosphine and 1-chloro-2-(2,4,6-tri- t -butylphenyl)-2-phosphaethenyllithium and utilized for complex formations as a ligand of the corresponding carbonyl-tungsten(0) complexes.     

Complexes of Co(II), Ni(II), and Cu(II) with (Z)-10-(2-(4-Amino-5-Thioxo-4,5-Dihydro-1H-1,2,4-Triazol-3-yl)hydrazono)-9-Phenanthrone: Synthesis,Spectral Studies,and Quantum Chemical Simulation of the Structures

Russian Journal of Coordination Chemistry - The complexes of (Z)-10-(2-(4-amino-5-thioxo-4,5-dihydro-1Н-1,2,4-triazol-3-yl)hydrazono)-9-phenanthrone (HL) with the Co(II), Ni(II), and Cu(II)...     

Synthesis and characterization of (Z)-5-arylmethylidene-rhodanines with photosynthesis-inhibiting properties

A series of rhodanine derivatives was prepared. The synthetic approach, analytical and spectroscopic data of all synthesized compounds are presented. Lipophilicity of all the discussed rhodanine derivatives was analyzed using the RP-HPLC method. The compounds were tested for their ability to inhibit photosynthetic electron transport (PET) in spinach (Spinacia oleracea L.) chloroplasts and reduce chlorophyll content in freshwater alga Chlorella vulgaris. Structure-activity relationships between the chemical structure, physical properties and biological activities of the evaluated compounds are discussed. For majority of the tested compounds the lipophilicity of the compound and not electronic properties of the R1 substituent were decisive for PET-inhibiting activity. The most potent PET inhibitor was (5Z)-5-(4-bromobenzylidene)-2-thioxo-1,3-thiazolidin-4-one (IC(50) = 3.0 μmol/L) and the highest antialgal activity was exhibited by (5Z)-5-(4-chlorobenzylidene)-2-thioxo-1,3-thiazolidin-4-one (IC(50) = 1.3 μmol/L).     

Preparation, properties, and catalytic activity of transition-metal complexes containing a ligated 2-methyl-3,3-diphenyl-1,3-diphosphapropene skeleton

2-Methyl-3,3-diphenyl-1-(2,4,6-tri-t-butylphenyl)-1,3-diphosphapropene behaved as an unsymmetrical chelating ligand for transition metal complexes and the 1,3-diphosphapropene moiety was hydrolyzed to afford the 1,3-diphosphapropan-1-ol derivative upon coordination. The palladium complex showed catalytic activity for the Sonogashira coupling reaction.     

Polydentate N(2)S(2)O and N(2)S(2)O(2) Ligands as Alcoholic Derivatives of (N,N'-Bis(2-mercaptoethyl)-1,5-diazacyclooctane)nickel(II) and (N,N'-Bis(2-mercapto-2-methylpropane)-1,5-diazacyclooctane)nickel(II)

The synthesis, structural characterization, spectroscopic, and electrochemical properties of N(2)S(2)-ligated Ni(II) complexes, (N,N'-bis(2-mercaptoethyl)-1,5-diazacyclooctane)nickel(II), (bme-daco)Ni(II), and (N,N'-bis(2-mercapto-2-methylpropane)1,5-diazacyclooctane)nickel(II), (bme-daco)Ni(II), derivatized at S with alcohol-containing alkyl functionalities, are described. Reaction of (bme-daco)Ni(II) with 2-iodoethanol afforded isomers, (N,N'-bis(5-hydroxy-3-thiapentyl)-1,5-diazacyclooctane-O,N,N',S,S')halonickel(II) iodide (halo = chloro or iodo), 1, and (N,N'-bis(5-hydroxy-3-thiapentyl)-1,5-diazacyclooctane-N,N',S,S')nickel(II) iodide, 2, which differ in the utilization of binding sites in a potentially hexadentate N(2)S(2)O(2) ligand. Blue complex 1 contains nickel in an octahedral environment of N(2)S(2)OX donors; X is best modeled as Cl. It crystallizes in the monoclinic space group P2(1)/n with a = 12.580(6) ?, b = 12.291(6) ?, c = 13.090(7) ?, beta = 97.36(4) degrees, and Z = 4. In contrast, red complex 2 binds only the N(2)S(2) donor set forming a square planar nickel complex, leaving both -CH(2)CH(2)OH arms dangling; the iodide ions serve strictly as counterions. 2 crystallizes in the orthorhombic space group Pca2(1) with a = 15.822(2) ?, b = 13.171(2) ?, c = 10.0390(10) ?, and Z = 4. Reaction of (bme-daco)Ni(II) with 1,3-dibromo-2-propanol affords another octahedral Ni species with a N(2)S(2)OBr donor set, ((5-hydroxy-3,7-dithianonadiyl)-1,5-diazacyclooctane-O,N,N',S,S')bromonickel(II) bromide, 3. Complex 3 crystallizes in the orthorhombic space group Pca2(1) with a = 15.202(5) ?, b = 7.735(2) ?, c = 15.443(4) ?, and Z = 4. Complex 4.2CH(3)CN was synthesized from the reaction of (bme-daco)Ni(II) with 1,3-dibromo-2-propanol. It crystallizes in the monoclinic space group P2/c with a = 20.348(5) ?, b = 6.5120(1) ?, c = 20.548(5) ?, and Z = 4.     

Selenium heterocycles. XXXVII . Synthesis of 4-(thiazol-4-yl)-1,2,3-selenadiazoles and 4-(selenazol-4-yl)-1,2,3-selenadiazoles

Starting from readily available 2-substituted-4-formylthiazoles and selenazoles, a series of 4-(2-aryl-4-selenazolyl)-1,2,3-selenadiazoles I and 4-(2-substituted-4-thiazolyl)-1,2,3-selenadiazoles II were prepared. Pyrolysis of compound II afforded (2-substituted-4-thiazolyl) acetylenes VII. Addition of potassium hydroxide pellets to an alcoholic solution of II gave 2-substituted-1,4-diselenafulvenes VIII. Decomposition of compound II with base followed by the addition of carbon disulfide gave 5-substituted 2-thioxo-1,3-thiaselenoles XI.     

Zero-Crossing Derivative Spectrophotometric Determination of Mercury(II) And Palladium(II) with 5-(3,4-Methoxyhydroxyphenylmethylene)-2-thioxo-1-3-thiazolidine and Cetyltrimethylammonium Bromide

Abstract

A method is proposed for the simultaneous determination of mercury(II) and palladium(II) by first-derivative spectrophotometry based on the absorption spectra of their complexes with 5-(3,4-Methoxyhydroxyphenylmethylene)-2-thioxo-1,3-thiazolidine [5-(3,4-methoxyhydroxybenzylidene) rhodanine]. Zero-crossing measurement technique is found suitable for the measurement of the first-derivative value at the specified wavelengths. Mercury(II) (0.4-1.4 μg ml^?1) and palladium(II) (0.08 - 1.8 μg ml^?1) in different ratios have been determined simultaneously. A critical evaluation of the proposed method is performed by statistical analysis of the experimental data.     

(E)-[4,4,4-Trifluor-1-(trifluormethyl)-1,3-bis(trimethylsiloxy)-2-butenyl]diphenylphosphin als Ligand

The Ligand (E)-[4,4,4-Trifluoro-1-(trifluoromethyl)-1,3-bis(trimethylsiloxy)-2-butenyl]di-phenylphosphine The tertiary phosphine (E)-Ph₂PC(OSiMe₃)(CF₃)CH = C(OSiMe₃)CF₃ (L), 1 and the carbonyl Fe₂(CO)₉ react to give (OC)₄FeL, 2. Bis( 1,1,1,5,5,5-hexafluoropentane-2,4-dionato)palladium(II) and 1 furnish the diphenylphosphido group bridged palladium(II) complex 3 crystallizing from chloroform triclinic in the space group P1 with a = 12.600(3), b = 13.298(3), c = 13.975(3) Å, α = 93.27(2), β = 111.67(2), γ = 106.71(2)° The elementary cell contains Z = 2 formular units and two molecules CHCl₃ with two independent molecules 3 each showing an inversion centre. The planar [PdP], four membered ring system and the planar chelate units, exhibit a torsional angle of 6.75°     

Multiple pathways in the synthesis of new annelated analogues of 6-benzyl-1-(ethoxymethyl)-5-isopropyluracil (emivirine)

Condensation of 3-(3,5-dimethylphenyl)-2-oxocyclopentanecarboxamide (11) with oxalyl chloride and condensation of ethyl 2-benzylamino-5-methyl-3-phenylcyclopent-1-enecarboxylate (17a) with trimethylsilyl isothiocyanate gave 7-(3,5-dimethylphenyl)-6,7-dihydro-5H-cyclopenta[e][1,3]oxazine-2,4-dione (12) and 1-benzyl-5-methyl-7-phenyl-2-thioxo-1,2,3,5,6,7- hexahydrocyclopentapyrimidin-4-one (18a), respectively. Acid catalyzed ring-closure of 6-(4-methyl-1-phenylpent-3-enyl)-2-thioxo-2,3-dihydro-1H-pyrimidin-4-one (26) and radical mediated ring-closure of 1,3-bis(benzyloxymethyl)-5-bromo-6-(1-phenylbut-3-enyl)-1H-pyrimidine-2,4- dione (32a) gave 5,5-dimethyl-8-phenyl-5,6,7,8-tetrahydro-1H-quinazoline-2,4- dione (28) and 1,3-bis(benzyloxymethyl)-5-methyl-7-phenyl-1,5,6,7- tetrahydrocyclopentapyrimidine-2,4-dione (33), respectively. Annelated emivirine analogues 7-(3,5-dimethylphenyl)-1- ethoxymethyl-1,5,6,7-tetrahydrocyclopentapyrimidine-2,4-dione (4), 1-ethoxymethyl-5,5-dimethyl-8-phenyl-5,6,7,8-tetrahydro-1H-quinazoline- 2,4-dione (5) and 1-ethoxymethyl-5-methyl-7-phenyl-1,5,6,7- tetrahydrocyclopentapyrimidine-2,4-dione (6) were obtained in few steps from 12, 28 and 18a/33, respectively. These new analogues can be considered as conformationally locaTed analogues of emivirine. However, the compounds 4 6 showed lower activities against HIV-1 than emivirine and it is concluded that the locked conformation disfavours activity against HIV-1.     

New 1:3 type nickel-bis(dithiolene) salt (FcCHCHPymCH3)[Ni(dmit)2]3 (dmit: 2-thioxo-1,3-dithiole-4,5-dithiolate): its electrocrystallization, crystal structure, electrical properties, and electronic band structure analysis

Black single crystals of Ni(dmit)(2) complex (dmit: 2-thioxo-1,3-dithiole-4,5-dithiolate) with trans-4-[2-(1-ferrocenyl)vinyl]-1-methylpyridinium chromophore as a countercation, (FcCHCHPymCH(3))[Ni(dmit)(2)](3), were prepared by the electrocrystallization technique. In the triclinic structure of the complex (P, a = 11.430(5) A, b = 13.349(2) A, c = 19.355(6) A, alpha = 75.15(2) degrees , beta = 79.19(3) degrees , gamma = 82.12(2) degrees , Z = 2), Ni(dmit)(2) anion layers are separated by the cations with a relatively rare 1:3 cation-to-anion ratio. Detailed crystal and electronic structure analysis revealed that the anions are stacked in the layers to form alternating dimers and monomers rather than trimers. The measured electrical conductivity indicates a semiconducting property of the compound with an estimated energy gap of 0.06 eV. The calculated LUMO bands are very narrow, and the semiconducting behavior is more likely due to the electron localization mainly on the dimers, consistent with the observed longer Ni-S bond distances in the dimers.     

Ruthenium(II) porphyrin catalyzed formation of (Z)-4-alkyloxycarbonyl- methylidene-1,3-dioxolanes from gamma-alkoxy-alpha-diazo-beta-ketoesters

[reaction: see text] Ruthenum(II) porphyrins and dirhodium(II) acetate catalyze cyclization of gamma-alkoxy-alpha-diazo-beta-ketoesters to (Z)-4-(alkyloxycarbonylmethylidene)-1,3-dioxolanes selectively (ca. 68% yield) with no formation of 3(2H)-furanones. Reacting a diazo ketoester with [Ru(II)(TTP)(CO)] [H(2)TTP = meso-tetrakis(p-tolyl) porphyrin] in toluene afforded a ruthenium carbenoid complex, which has been isolated and spectroscopically characterized. A mechanism involving hydrogen atom migration from the C-H bond to the ruthenium carbenoid is proposed.     

The first structurally authenticated alkali metal 1,3-diphosphaallyl complex [[Bu(t)C(PMes)2]Li(thf)3] (Mes = 2,4,6-Me3C6H2): an alternative synthetic approach to substituted 1,3-diphosphaallyl complexes

Reaction of the phosphavinyl Grignard reagent [Z-MesP=C(Bu(t))MgBr.OEt2]2 (Mes = 2,4,6-Me3C6H2) with MesPCl2 affords the corresponding 1,3-diphosphapropene compound [Z-MesP=C(Bu(t))P(X)Mes] (X = Cl, Br); subsequent reaction with two equivalents of elemental lithium in thf affords the title compound [[Bu(t)C(PMes)2]Li(thf)3], which contains an asymmetric eta1-1,3-diphosphaallyl ligand.     

Synthesis of 2H-Thiopirano[3,4-c]pyrazol-7-one Derivatives as the First Example a New Heterocyclic System

Russian Journal of General Chemistry - A series of ethyl 4-[(Z)-(4-oxo-2-thioxo-1,3-thiazolidin-5-ylidene)methyl]-1-aryl-1H-pyrazole-3-carboxylates was obtained as a result of the reaction of ethyl...     

The unprecedented preparation of dinuclear zinc(II) complexes from 4-halido-2-[(3-cyclohexylaminopropylimino)methyl]phenol

Three new centrosymmetric trinuclear nickel(II) and manganese(II) complexes, Ni[Ni(CH(3)COO)(CPA)](2) (1), Ni[Ni(CH(3)COO)(BPA)](2) (2), Mn[Mn(CH(3)COO)(BPA)](2) (3), where H(2)CPA = N,N'-bis(5-chlorosalicylidene)-1,3-propanediamine, H(2)BPA = N,N'-bis(5-bromosalicylidene)-1,3-propanediamine, and two new centrosymmetric dinuclear zinc(II) complexes, [Zn(2)(CMP)(2)] (4) and [Zn(2)(BMP)(2)] (5), where H(2)CMP = 4-chloro-2-{[3-(5-chloro-2-hydroxybenzyl)aminopropylimino]methyl}phenol, and H(2)BMP = 4-bromo-2-{[3-(5-bromo-2-hydroxybenzyl)aminopropylimino]methyl}phenol, have been prepared from the Schiff bases derived from 5-halido-substituted salicylaldehydes with N-hexylpropane-1,3-diamine under solvothermal conditions. The complexes have been characterised by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction studies. The complexes 1, 2, and 3 crystallise in the monoclinic space group P2(1)/c with cell dimensions a = 9.347(1), b = 11.507(2), c = 18.539(2) ?, β = 93.774(2)°, Z = 2 (for 1), a = 9.111(4), b = 12.089(6), c = 18.724(8) ?, β = 92.117(7)°, Z = 2 (for 2), and a = 11.328(2), b = 22.468(5), c = 8.270(2) ?, β = 93.74(3)°, Z = 2 (for 3), while complexes 4 and 5 crystallise in the triclinic space group P1, with cell dimensions a = 7.483(1), b = 9.990(2), c = 12.155(2) ?, α = 75.27(3), β = 85.00(3), γ = 73.82(3)°, Z = 1 (for 4), and a = 7.008(1), b = 10.081(2), c = 13.095(3) ?, α = 100.62(3), β = 95.51(3), γ = 104.03(3)°, Z = 1 (for 5). It is interesting that the mono-Schiff bases 4-chloro-2-[(3-cyclohexylaminopropylimino)methyl]phenol (HCCP) and 4-bromo-2-[(3-cyclohexylaminopropylimino)methyl]phenol (HBCP) used to prepare the nickel(II) and manganese(II) complexes were transferred to bis-Schiff bases H(2)CPA and H(2)BPA in the complexes 1, 2, and 3, while the mono-Schiff bases HCCP and HBCP used to prepare the zinc(II) complexes were transferred to novel ligands H(2)CMP and H(2)BMP, bearing the unexpected, newly formed carbon-nitrogen single bond.     

Extensively Conjugated Dianionic Tetrathiooxalate-Bridged Copper(II) Complexes for Synthetic Metals

Using a unique three-solvent biphasic method, we have prepared and characterized three new fully conjugated, chalcogen-rich, bridged copper(II) complexes for the preparation of molecular conductors and magnetic materials, having the general formula (Bu(4)N)(2){tto[Cu(L)](2)} (tto = C(2)S(4)(2)(-) = tetrathiooxalato; L = mnt = C(4)N(2)S(2)(2)(-) = 1,2-dicyanoethene-1,2-dithiolato for complex 2, dsit = C(3)Se(2)S(3)(2)(-) = 2-thioxo-1,3-dithiole-4,5-diselenolato for complex 3, dmid = C(3)OS(4)(2)(-) = 2-oxo-1,3-dithiole-4,5-dithiolato for complex 4a). The single-crystal X-ray structures of 2 and 3 have been determined: 2, (Bu(4)N)(2){tto[Cu(mnt)](2)}, monoclinic, space group C2/m, a = 19.549(4) ?, b = 13.519(3) ?, c = 10.162(2) ?, beta = 90.33(1) degrees, Z = 2; 3, (Bu(4)N)(2){tto[Cu(dsit)](2)}, monoclinic, space group P2(1)/c, a = 9.903(1) ?, b = 15.589(1) ?, c = 18.218(1) ?, beta = 90.40(1) degrees, Z = 2. Complex 2 displays perfect planarity, while 3 shows a slight tetrahedral distortion at the metal centers, resulting in a dihedral angle of 24.86(3) degrees. Cyclic voltammetry of (Bu(4)N)(2){tto[Cu(mnt)](2)} (2), (Bu(4)N)(2){tto[Cu(dsit)](2)} (3), and (Bu(4)N)(2){tto[Cu(dmid)](2)} (4a) shows each complex to exhibit two reversible redox processes which can be attributed to {tto[Cu(L)](2)}(2)(-) right arrow over left arrow tto[Cu(L)](2)}(-) and {tto[Cu(L)](2)}(1)(-) right arrow over left arrow {tto[Cu(L)](2)}(0) couples. The structural and electronic properties of 2, 3, and 4a will be compared to those of the recently communicated analogous complex (Bu(4)N)(2){tto[Cu(dmit)](2)} (1).     

Synthesis,Crystal Structure and Fluorescence of a Three-dimensional Cd(II) Coordination Polymer [Cd(μ_(1,3)- SCN~-)_2(μ-dmpo)]_n (dmpo = 3,5-Dimethylpyridine N-Oxide)

1 INTRODUCTION For a long time much research interest has been focused on coordination polymeric compounds[1] be- cause they may afford new materials with useful properties, such as catalytic activity, micro-porosity, electrical conductivity, non-linear optical activity, magnetic coupling behavior and so on[2]. Thiocya- nate anion, pyridine N-oxide and its derivatives be- long to very useful bridge ligands and many com- plexes[3～5] with one of them as bridge ligand exhibit special propert…     

(E)- and (Z)-1-benzenesulfonyl-4-trimethylsilyl-2-butenes as (E)-1-(1,3-butadienyl) synthons

(E)- and (Z)-1-benzenesulfonyl-4-trimethylsilyl-2-butenes (E/Z=9), prepared from 4-trimethylsilyl-1-buten-3-ol, $\text{n}$-butyllithium and benzenesulfenyl chloride and oxidation of the intermediate (E)- and (Z)-1-benzenesulfinyl-4-trimethylsilyl-2-butenes with hydrogen peroxide, react with $\text{n}$-butyllithium and then primary halides to give 4-benzenesulfonyl-1-trimethylsilyl-2-alkenes which are rapidly 1,4-debenzenesulfonyltrimethylsilated to (E)-1,3-alkadienes by tetra-$\text{n}$-butylammonium fluoride at O°C.