Two Novel Heterothiometallic Clusters Modified by 1,1′-Bis(diphenylphosphino) ferrocene (dppf) in Quasi-Closed Bridging Mode: Syntheses, Structures and Properties

Two heterothiometallic clusters modified by 1,1′-bis(diphenylphosphino) ferrocene (dppf) ligand [(Ag₄Mo₂S₈)(dppf)₂] (1) and [(Ag₄Mo₂S₆O₂)(dppf)₂] (2) have been synthesized and characterized. X-ray single-crystal studies reveal that the structures of the two clusters are both hexagonal prism-shaped cages, which are modified by dppf ligands in rarely quasi-closed mode. While, the terminal atoms of the hexagonal prism cages are different, S atoms for 1 and O atoms for 2. The discrete clusters of 1 and 2 are connected to form 2-D supramolecular layers through hydrogen bonds C–H···S, C–H···π for 1 and C–H···O for 2. The different supramolecular interactions may be caused by the different terminal atoms, which also result in different fluorescence emissions and oxidation potentials.     

Synthesis and Crystal Structure of Dibromo [1,1′- bis(diphenylphosphino)ferrocene]cadmium(II)

1 INTRODUCTION The transition metal complexes containing ferrocene ligand arouse the interest of chemists because of their novel structures and special properties[1]. The ferrocene derivatives have been used in electrochemistry, in nonlinear optics, and as molecular ferromagnets. Some complexes of 1,1′-bis(diphenylphosphino)ferrocene (dppf) have been synthesized, and many of their crystal structures have been reported by far[2~5]. Here we report the synthesis and crystal structure of a …     

Solvent-dependent conformational polymorphism in the crystal structure of mercuric bromide adduct of 1,1′-bis(diphenylphosphino)ferrocene

Two polymorphs of dinuclear mercury–iron complexes, [HgBr₂(dppf)] (1) where dppf is 1,1′-bis(diphenylphosphino)ferrocene, are prepared and crystal structures are determined by X-ray crystallography. The reaction of mercury(II) bromide with dppf in methanol–dichloromethane led to orange block polymorph. After crystallization of this complex in DMSO, a red needle polymorph was obtained.     

Preparation of a series of NiL(η2-C60) complexes (L = 1,2-bis(diphenylphosphino)ethane,and 1,1′-bis(diphenylphosphino)ferrocene) by zinc dust reduction

A simple method for preparation of nickel-fullerene coordination complexes has been developed. NiLCl₂(Br₂) and C₆₀ mixtures are reduced by zinc dust upon heating in o-dichlorobenzene. Diffusion of hexane into the reaction mixture results in formation of crystals of NiL(η²-C₆₀)?solvent (L = 1,2-bis(diphenylphosphino)ethane (dppe, 1), 1,3-bis(diphenylphosphino)propane (dppp, 2) and 1,1′-bis(diphenylphosphino)ferrocene (dppf, 3)). Nickel coordinates to the 6–6 bonds of C₆₀ by η²- type and has distorted square-planar geometry. The average Ni–C(C₆₀) bond lengths are 1.936(6)–1.977(3)?Å. We found that increase in the P(L)–Ni–P(L) angle and the dihedral angle between the PNiP and CNiC planes results in elongation of the Ni–C(C₆₀) and Ni–P(L) bonds by 0.04–0.06?Å. Complexes 1–3 contain zero-valent nickel since fullerenes are neutral according to the IR- and visible-NIR spectra. Some of the IR-active bands of C₆₀ are split into three bands in spectra of 1–3 due to C₆₀ symmetry lowering, and the F_1u(4) C₆₀ mode is shifted to lower wave numbers due to the π-back donation. The formation of 1–3 is accompanied by appearance of new bands in the visible range at 435–447 and 661–680 nm.     

Tin,palladium and platinum derivatives of 1,1′-bis(diphenylphosphine)ferrocene. Crystal and molecular structures of 1,1′- bis-(diphenylphosphine)ferrocenedichloropalladium(II) and of 1,1′-bis(diphenylphosphine)ferrocenedichloroplatinum(II)

Summary Ten derivatives of 1,1-bis(diphenylphosphine)ferrocene (BDPF) are described in this paper. The first three, [BDPF·SnCl₄] (1), [BDPF·MeSnCl₃] (2) and [BDPF·PhSnCl₃] (3), present the two phosphorus atoms of the ligand directly bonded to a Sn centre. Two others, [BDPF-PdCl₂ (4) and [BDPF·PtCl₂] (5), similarly have the ligand BDPF acting as a bidentate species towards a transition metal. The crystal and molecular structures of (4) and (5) are presented here. Two other BDPF complexes were obtained with Pd and Pt, with the transition metals in the zerovalent state, namely [Pd(BDPF)₂] (6) and [Pt(BDPF)₂] (7). Finally, three trimetallic complexes are also described; [BDPF·Pd(-Cl)₂SnCl₂] (8), [BDPF· Pt(-Cl)₂SnCl₂] (9) and [BDPF·PdClSnCl₃] (10).     

Synthesis and applications of (R)- and (S)-7,7′-dimethoxy-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene

The synthesis of (R)- and (S)-7,7′-dimethoxy-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene 5a and 5b is described. The phosphorus atoms in (S)-(−)-5b are shown to be slightly more basic than the phosphorus atoms in (S)-BINAP by comparing the magnitude of the ¹J (³¹P–⁷⁷Se) coupling constant in their respective diselenide derivatives. (S)-(−)-5b behaved similarly to (S)-BINAP in asymmetric Heck reactions.     

Standard molar enthalpies of formation and phase changes of Tetra-N-phenylbenzidine and 4,4′-Bis (N-carbazolyl)-1,1′-biphenyl

Journal of Thermal Analysis and Calorimetry - The values of the standard molar energies of combustion of Tetra-N-phenylbenzidine and 4,4′-Bis(N-carbazolyl)-1,1′-biphenyl in solid phase...     

Dithiocarbamate Complexes of Nickel(II) with 1,1′-Bis(Diphenylphosphino) Ferrocene

Ni(II) complexes of composition [Ni(bzⁱprdtc)(dppf)]X, [Ni(but₂dtc)(dppf)]X and [Ni(Rdtc)(dppf)]X [bz = C₇H₇; ⁱpr = C₃H₇; but = C₄H₉; R = pld = C₄H₈; tz = C₃H₆S; hmi = C₆H₁₂; dtc = S₂CN; dppf = 1,1'-bis(diphenylphosphino)ferrocene C₃₄H₂₈P₂Fe; X = ClO₄, I, Br, NCS] were synthesized and characterized X-ray structural analysis of [Ni(hmidtc)(dppf)]ClO₄ confirmed coordination number four for nickel in a distorted, square-planar, NiS₂P₂ arrangement     

Thermodynamics of dissolution of acetoacetyl and 1,1′-bis(acetoacetyl)ferrocene in water-tert-butanol solutions

The polythermal solubility of acetoacetylferrocene and 1,1′-bis(acetoacetyl)ferrocene (bis(acac)Fec) in water-tert-butanol solutions of different composition was studied. The solubility of the substances under study (to a greater extent, for acetoacetylferrocene) increases with rising temperature and alcohol content. Two dissolution mechanisms, the void and solvation mechanisms, were proposed. The thermodynamic parameters of dissolution and transfer of the solute substances from water to the mixed solvent of a certain composition were estimated.     

Synthesis and liquid crystalline behavior of a series of ferrocene 1,1′-bis-azino-derivatives

A series of liquid-crystalline ferrocene derivatives, Fe{C₅H₄-C(CH₃)=N-N=CH-C₆H₃(X)-OOC-C₆H₄-OC _n H_2n+1}₂ (X = H, OH;n = 3 to 12), were obtained by the condensation of 1,1 -bishydrazondiacetylferrocene withp-alkoxybenzoyloxybenzaldehides. According to DSC and polythermic microscopy, all of the compounds exhibit an enantiotropic nematic mesophase in the 150–230 °C temperature range. A polycrystalline transition precedes the nematic transition. The liquid crystalline properties of the obtained compounds were investigated with respect to the number of carbon atoms in the terminal alkyl chain and the terminal hydroxyl group. The composition and structure of the obtained compounds were determined by elemental analysis and IR and NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 358–361, February, 1995.This work was carried out with financial support from the Russian Fundation for Basic Research (Project No. 94-03-08978).     

Synthesis, Structure and Electrochemistry of Macrocyclic 1,1＇-Bis（1,3-phenyleneoxyacetylpyrazoyl）ferrocene

1,1＇-Diacetoacetylferrocene 1 reacted with phenylene-1,3-dioxyactyl hydrazine 2 in absolute ethanol to give the macrocyclic ferrocenyl dipyrazole compound in moderate yield. Determined by X-ray structure analysis, it crystallizes in monoclinic system, space group P21/c with a = 13.7509（4）, b = 8.1277（2）, c = 21.7472（6） A, β = 103.1030（10）°, V = 2367.25（11） A^3, Z = 4, Dc = 1.505 g/cm^3, R = 0.0353 and wR = 0.0811. The electrochemical studies reveal that redox of Fe^＋/Fe in ferrocene is a reversible one-electron process.     

Synthesis and characterization of some ferrocene-containing telluroether ligands: crystal structure of 1,1′-bis(phenyltelluro)ferrocene

A series of five monodentate ferrocene tellurium ligands of the type Fe(C₅H₅)(C₅H₄TeR) and five bidentate 1,1′-disubstituted ferrocene tellurium ligands of the type Fe(C₅H₄TeR)₂ (R = Me, ⁿBu, C₆H₅, p-MeOC₆H₄, p-EtOC₆H₄) has been prepared by the reaction of 1,1′-dilithioferrocene with the appropriate ditellurides R₂Te₂. The ligands have been characterized by their elemental analyses, ¹H and ¹³C NMR spectra, mass spectra and cyclic voltammetry studies. The structure of Fe(C₅H₄TeC₆H₅)₂ has been determined by single-crystal X-ray diffraction study.     

Temperature dependences of the solubility of acetoacetylferrocene and 1,1′-bis(acetoacetyl)ferrocene in water-methanol mixed solvents

The solubility of β-dicarbonyl derivatives of ferrocene (acetoacetylferrocene and 1,1′-bis(acetoacetyl)ferrocene) in water-methanol binary solvents at various temperatures is investigated over a wide range of compositions of the mixed solvent. It is established that the solubility of these substances increases (especially, acetoacetylferrocene) with the temperature and methanol fraction in the solvent. It is concluded that the dissolution of the ferrocene β-diketones is accompanied by positive changes in enthalpy and entropy.     

The Dissociation Constants of 1,1′-Bis (pyridinium-4-aldoxime)trimethylene dibromide

Summary. The dissociation constants of the two oxime groups of 1,1-bis(pyridinium-4-aldoxime)trimethylene dibromide (TMB-4) were determined using spectrophotometric data. Two numerical methods were applied to treat the overlapping equilibria. The results obtained by both agreed with each other and their mean values at 25°C corrected for the ionic strength of 0.05moldm^–3 are pK_a1=7.49±0.11 and pK_a2=8.96±0.09. These values were discussed in terms of the pK_as of 1,1-bis(pyridinium-4-aldoxime)oxydimethylene dichloride (Toxogonin), a similar dioxime, which were derived by extrapolation of literature data.     

Syntheses and Crystal Structures of Polynuclear Cu(I) Complexes Containing the 1,1′-Bis-(diphenylphosphino)-ferrocene Ligand

 The reaction between [Cu(NCMe)₄][PF₆] and 1,1′-bis-(diphenylphosphino)-ferrocene (dppf) in several ratios, solvents, and conditions led to the synthesis and structural characterization of the Cu(I) complexes [Cu(dppf)(Odppf)][PF₆] (1), [(dppf)Cu(μ-dppf)Cu(dppf)][PF₆]₂ (2), and [(dppf)Cu(μ-Cl)₂Cu(dppf)] (3). Although 1 and the cation in 2 were known, the first was structurally characterized for the first time, exhibiting a significant asymmetry in the coordination sphere of Cu(I) owing to the presence of oxygen. In 2, the PF₆ ⁻ anion led to an interesting crystal packing with large open channels containing water. Finally, DFT calculations on a model of 3 showed that its HOMO exhibits, besides Fe, a significant Cu and Cl character, which is reflected in its electrochemical properties.     

Syntheses and Crystal Structures of Polynuclear Cu(I) Complexes Containing the 1,1′-Bis-(diphenylphosphino)-ferrocene Ligand

Summary.  The reaction between [Cu(NCMe)₄][PF₆] and 1,1′-bis-(diphenylphosphino)-ferrocene (dppf) in several ratios, solvents, and conditions led to the synthesis and structural characterization of the Cu(I) complexes [Cu(dppf)(Odppf)][PF₆] (1), [(dppf)Cu(μ-dppf)Cu(dppf)][PF₆]₂ (2), and [(dppf)Cu(μ-Cl)₂Cu(dppf)] (3). Although 1 and the cation in 2 were known, the first was structurally characterized for the first time, exhibiting a significant asymmetry in the coordination sphere of Cu(I) owing to the presence of oxygen. In 2, the PF₆ ⁻ anion led to an interesting crystal packing with large open channels containing water. Finally, DFT calculations on a model of 3 showed that its HOMO exhibits, besides Fe, a significant Cu and Cl character, which is reflected in its electrochemical properties. Received July 14, 2000. Accepted July 21, 2000     

8,8′-Bis(diphenylphosphinomethyl)-1,1′-binaphthyl. Synthese und Konformation

Summary The title compound3 was prepared from 8,8-Bis(bromomethyl)-1,1-binaphthyl (1) in two steps in approx. 10% overall yield. The crystal structure of the intermediate phosphinoxide2 was determined. Attempts to prepare chelate complexes of3 with Ni(II) or Pd(II) failed.

     

Constants of keto-enol equilibrium of acetoacetyl- and 1,1′-bis(acetoacetyl)ferrocene in aprotic solvents at 20°

The keto-enol equilibrium of 2 × 10⁻³ M solutions of (acetoacetyl)ferrocene and 1,1′-bis(acetoacetyl)ferrocene was studied by ¹H NMR spectroscopy in a series of aprotic solvents such as DMSO-d ₆, (CD₃)₂CO, CDCl₃, CD₂Cl₂, CCl₄, and C₆D₆ at a temperature of 20°C. It was established that the calculated enolization constants increase with a decrease in the polarity of solvent molecules. The results complement and combine known empirical rules about the effect of the medium on keto-enol equilibria.     

Ligand substitution reaction of (μ-H)Os3(CO)10(μ-COMe) with 1,1'-bis(diphenylphosphino) ferrocene

Reaction of (μ-H)Os₃(CO)₁₀(μ-COMe) with 1,1'-bis(diphenylphosphino)-ferrocene (dppf) produces (μ-H)Os₃(CO)₈(μ-COMe){μ-η²-(η⁵-C₅H₄PPh₂)₂Fe} (1) and (μ-H)₂Os₃(CO)₇(μ-COMe){μ-η³-(η⁵-C₅H₃PPh₂)Fe(η⁵-C₅H₄PPh₂)} (2). Thermolysis of 1 leads quantitatively to 2. These compounds have been characterized by ¹H, ³¹P, and ¹³C NMR, IR, and mass spectroscopies. Compound 2 crystallizes in space group P 2₁/c with a = 11.898(2), b = 21.266(3), c = 18.262(3) Å, β = 104.71(1)°, V = 4469(1) ų, Z = 4, and R_F = 0.029.     

Role of the transition metal complexes of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) in asymmetric catalysis

Metal complexes of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) are being used as a chiral catalysts in many organic reactions. This review highlights recent developments on synthesis of metal BINAPs and its application in various organic synthesis. The studies done on the application of metal BINAPs show a unique reactivity, which enables its use in entirely different sets of chemical transformation.