Synthesis,characterization and evaluation of heterobimetallic Fe(II)/Rh(I) and Fe(II)/Ru(II) complexes as catalyst precursors for hydroformylation of 1-octene

Abstract

Two new ferrocenyl iminopyridyl ligands, L1 and L2, have been synthesized and characterized using spectroscopic and analytical techniques. Both ligands were used to prepare new Rh(I) and Ru(II) ferrocenyl complexes 1–4. The structures of the complexes were confirmed using ¹H and ¹³C nuclear magnetic resonance spectroscopy, high resolution electrospray ionization mass spectrometry, and infrared spectroscopy. The complexes were tested as catalysts in the hydroformylation of 1-octene. Rh ferrocenyl complexes 1 and 4 produced aldehydes under mild conditions while the Ru-ferrocenyl complexes 2 and 3 required higher temperature and pressure for effective hydroformylation to occur. The catalysts display excellent aldehyde chemoselectivity with varying regeoselectivity depending on temperature and pressure conditions employed. At high temperatures, the Rh ferrocenyl precatalysts favor formation of branched aldehydes due to increased isomerization at high temperatures. The Ru ferrocenyl precatalysts displayed less hydroformylation activity; however, the complexes show good chemoselectivity for aldehydes with no hydrogenation products formed.     

Über 2-(Dimethylaminomethyl)ferrocenyl-Verbindungen des Vanadiums,Niobs und Tantals

On 2-(Dimethylaminomethyl)ferrocenyl Compounds of Vanadium, Niobium, and Tantalum Former results, indicating the ability of (dimethylaminomethyl)ferrocenyl groups forming stable σ-organo transition-metal derivatives, were proved by the synthesis of heterobimetallic 2-(dimethylaminomethyl)ferrocenyl compounds of the three-valued vanadium as well as five valued niobium and tantalum from VCl₃, NbCl₅, TaCl₅, and (FcN)Li ( I ). The synthesis and properties of the compounds (FcN)₂VCl ( II ), (FcN)_nNbCl_5–n(THF)_x [n = 1, x = 1,3 ( III ); n = 2, x = 0 ( IV ); n = 3, x = 0 ( V )] as well as (FcN)TaCl₄(THF)_1.5 ( VI ) are reported. An intensive characterization, especially in respect of possible chelate structures was tried by i.r., ¹H-n.m.r., uv-vis, mass spectroscopy, and elementary analysis.     

Syntheses,spectroscopic, and magnetic properties of polystyrene-anchored coordination compounds of tridentate ONO donor Schiff base

The crosslinked chloromethylated polystyrene (PSCH₂–Cl) reacts with the Schiff base, derived from condensation of PSCH₂–Cl with 3-formylsalicylic acid and salicylhydrazide to form a polystyrene-anchored Schiff base, PSCH₂–LH₃ (1). Compound 1 reacts with a number of metal ions to form polystyrene-anchored coordination compounds, PSCH₂–LHM?·?DMF (where M?=?Cu, Zn, Cd, UO₂, and MoO₂), PSCH₂–LHM′?·?3DMF (where M′?=?Mn, Co, and Ni), PSCH₂–LHFeCl?·?2DMF, and PSCH₂–LHZr(OH)₂?·?2DMF. The polystyrene-anchored coordination compounds have been characterized by elemental analyses, spectra (infrared, reflectance, and electron spin resonance) and magnetic susceptibility measurements. The polystyrene-anchored compounds are magnetically dilute. Shifts in band positions of the groups involved in coordination have been utilized to find tridentate ONO donor behavior of 1. The polystyrene-anchored Zn(II), Cd(II), Zr(IV), MoO₂(VI), and UO₂(VI) compounds are diamagnetic, while Mn(II), Co(II), Ni(II), Cu(II), and Fe(III) compounds are paramagnetic. The polystyrene-anchored Cu(II) compound is square planar; Zn(II) and Cd(II) compounds are tetrahedral; Co(II), Ni(II), Mn(II), Fe(III), MoO₂(VI), and UO₂(VI) compounds are octahedral; and Zr(IV) compound is pentagonal bipyramidal.     

Syntheses,characterization of and studies on the electrochemical behaviour of ferrocenyl dithiophosphonates and 4-methoxyphenyl dithiophosphonates

Some 1,3-dithiadiphosphetane 2,4-disulfides (X₂P₂S₄, X: Fc, FcLR; X: CH₃O?C₆H₄?, LR) were allowed to react with alcohols to obtain dithiophosphonic acids (X(OR)PS₂H). These were converted to the corresponding ammonium salts. The salts were of the structures [Fc(OR)PS₂]^?[NH₄]⁺, R: 3-methyl-1-butyl- for I; 1-phenyl-1-propyl- for II; 3-pentyl- for III; 3-phenyl-1-propyl- for IV and [CH₃O?C₆H₄(OR)PS₂]^?[NH₄]⁺, R: 3-methyl-1-butyl- for V and 1-phenyl-1-propyl- for VI. To the best of our knowledge, all the compounds except V were prepared for the first time.

The compounds synthesized were characterized by elemental analysis, NMR (¹H, ¹³C, ³¹P), MS, FTIR, and Raman spectroscopies. Electrochemical behaviors of I–VI at disposable pencil graphite electrode (PGE) were investigated by using cyclic voltammetry (CV) and square-wave voltammetry (SWV). Adsorption and diffusion patterns of all the compounds on the PGE were also studied.

Two electroactive groups were identified in the compounds I–IV and only one in V and VI. The ferrocenyl groups of I-IV were oxidized at around 0.4 V. The same compounds display a second, more intense CV band at 0.8 V. The corresponding band for the compounds V–VI appears at around 0.6 V with a much weaker intensity. It is suggested that the ferrocenyl group introduced into the structures stabilizes the radical species formed as the product of the oxidation of the dithiophosphonato group.     

Beiträge zur Lanthanoidchemie. II. Zur Kenntnis von 2-(Dimethylaminomethyl)ferrocenyl-Verbindungen des Yttriums,Dysprosiums und Holmiums

Contributions to Organolanthanide Chemistry. II. On 2-(dimethylaminomethyl)ferrocenyl Compounds of Yttrium, Dysprosium, and Holmium Early reports about the ability of the 2-(dimethylaminomethy1)ferrocenyl group to form stable heterobimetallic organolanthanide(III) compounds have been confirmed by the synthesis of the organolanthanide(III) derivatives (C₅H₅)₂Ln(FcN) [Ln = Y (II), Dy (III), Ho (IV)], C₅H₅Dy(FcN)₂ · 2,5 THF (V) und C₅H₅Ln(FcN)Cl [Ln = Dy (VI), Ho (VII)] from the corresponding cyclopentadienyllanthanide(III) chlorides (C₅H₅)₂LnCl or C₅H₅LnCl₂ resp. and (FcN)Li (I). The products have been characterized by elemental analyses, IR-, ¹H-NMR, ¹³C-NMR and UV/Vis spectra as well as mass spectra and the determination of their effective magnetic moments.     

Synthesis and optical and electrochemical properties of glucose-cored ferrocenyl dendrimers

Triazole-based ferrocenyl glycoconjugates 1, 2, and 3 were synthesized by regiospecific copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) of azidoferrocenyl derivatives with glucose pentaacetylide. Higher generation ferrocenyl glycoconjugates form the stable ferrocenium cation and exhibit increased light harvesting property as revealed from cyclic voltammogram studies and ultraviolet–visible spectrum respectively due to the presence of more ferrocenyl and triazolyl units than the lower generation dendrimer.     

Preparation,Spectroscopic Properties and Characterization of Oxovanadium(IV), Isothiocyanatomanganese(III), Cyanocobalt(III) and Cobalt(II) Complexes with a Bis-Crown Ether Tetraaza[14]Annulene

Oxovanadium(IV), isothiocyanatomanganese(III), cyanocobalt(III) and cobalt(II) complexes of tetraaza[14]annulene appended with two crown ethers at 2,3- and 11,12-positions have been prepared. Cation complexation behavior of these cavity-bearing tetraaza[14]annulene complexes has been investigated by optical absorption methods. The cation K + , which necessitates two crown ether cavities for complexation, induces dimerization of the tetraaza[14]annulene complexes, whereas the Na + does not. Formation of the sandwich complexes due to dimerization is hindered by the steric interactions involving the axial ligand as judged by the blue shift of the intense band around 385-425 nm. Judging from its ESR spectrum, the cobalt(II) complex becomes a monomeric dioxygen complex of a 1 : 1 molar ratio in the presence of O 2 and pyridine at 77 K.     

Syntheses,Crystal Structures,and Properties of Two <Emphasis Type="Italic">d</Emphasis><Superscript>10</Superscript> Metal Complexes Based on Ferrocenyl Ligands Bearing Pyrazolyl Pyridine Substituents

Two new complexes, namely, [Cd₂(L¹)₂(NCS)₄(DMF)₂] · 4H₂O (I) and {[Zn₃(L²)₄(SO₄)₃(H₂O)₈] · 3DMF · 6H₂O} _n (II) have been synthesized through self-assembly of Cd(II) or Zn(II) salts with ferrocenyl ligands bearing pyrazolyl pyridine substituents. The two compounds were characterized by IR spectra, element analysis, X-ray powder diffraction, single-crystal X-ray diffraction (СIF files CCDC nos. 949526 (I), 949527 (II)), and thermogravimetric analysis. Complex I crystallizes in the monocline space group P21/c and exhibits a discrete dinuclear structure. The adjacent dinuclear molecules are packed into a 1D linear chain through the hydrogen-bond interactions. Complex II is a neutral one-dimensional infinite zigzag coordination chain. The 3D packing diagram of II contains two types of voids and the solvated DMF and water molecules filled them and stabilized by the hydrogen bonds. In addition, the redox properties of both complexes I and II have also been investigated.     

Propynylferrocene and (phenyl­ethyn­yl)­ferrocene

The title compounds, propynylferrocene, [Fe(C₅H₅)(C₈H₇)], (I), and (phenyl­ethyn­yl)ferrocene, [Fe(C₅H₅)(C₁₃H₉)], (II), are stabilized by weak C—H⋯π inter­actions. The C[triple‐bond]C bond distances in these mol­ecules are in the range 1.182 (3)–1.192 (3) Å. In (II), the ferrocenyl and phenyl groups are perpendicular, making an angle of 89.06 (13)°, which is a rare occurrence.     

二茂铁四唑和二茂铁甲醛缩3-取代丙二醇衍生物的合成

以甲酰基二茂铁6为原料, 通过与NH₄OH•HCl的缩合反应得到二茂铁肟7, 再经脱水剂脱水得到二茂铁腈8, 最后在(n-C₄H₉)₃SnCl的作用下与NaN₃反应生成新化合物二茂铁四唑(9). 以甲酰基二茂铁为原料, 在对甲苯磺酸(PTSA)的催化作用下与原甲酸三甲酯反应生成二甲基二茂铁缩醛(10), 然后与(R)-(－)-3-氯-1,2-丙二醇反应得到新的二茂铁缩醛衍生物12, 12再与NaN₃发生取代反应得到新的二茂铁缩醛衍生物13. 而新的二茂铁缩醛衍生物15的合成则是先由(R)-(－)-3-氯-1,2-丙二醇与CH₃OH在NaOH的作用下生成(R)-(－)-1-甲氧基-2,3-丙二醇(14), 再由14与二甲基二茂铁缩醛(10)反应得到的. 所合成的新化合物都用MS, ¹H NMR和IR谱确证了它们的结构.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 58. Zur Kenntnis von 2-(Dimethylaminomethyl)ferrocenyl-Verbindungen des Vanadiums,Molybdäns,Wolframs, Thoriums und Urans

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 58 On 2-(Dimethylaminomethyl)ferrocenyl Compounds of Vanadium, Molybdenum, Tungsten, Thorium, and Uranium Earlier results according to which dimethylaminomethylferrocenyl groups (FcN) are able to form stable organometallic chelate compounds were confirmed by synthesis of the heterobimetallic chelate compounds (FcN)₂VO · Li(acac) II , (FcN)MoO₂(acac) III , (FcN)WOCl₃ IV , (FcN)Th(acac)₃ V , and (FcN)UO₂(acac) VI from the corresponding metal acetylacetonates or oxidchlorides and (FcN)Li I . The new compounds were characterized by elemental analysis, the i.r., ¹H-n.m.r., and electron spectra and by their effective magnetic moments.     

Preparation,characterization and biological studies of some novel ferrocenyl compounds

Reaction of ferrocene with trichloroacetimidates in the presence of TMSOTf as a catalyst gave a series of novel ferrocenyl compounds, 1–7, in good yield and by a simple method using the Friedel–Crafts reaction. Only monosubstituted ferrocenyl compounds were obtained by flash chromatography at room temperature. Attempts to separate the disubstituted ferrocenyl compounds were unsuccessful, even in the presence of excess (2:1, 3:1 or 4:1) of trichloroacetimidates. The prepared compounds have been characterized by ¹H NMR, ¹³C NMR, IR, UV–vis and mass spectra as well as elemental analysis. The prepared compounds showed medium to good antimicrobial activity against Bacillus subtilis (+ve), Staphylococcus aureus (+ve), Candida albicans (yeast), Escherichia coli (?ve), Salmonella typhi (?ve), Aspergillus niger (fungi) and Fusarium solani (fungi). Copyright © 2005 John Wiley & Sons, Ltd.     

Comparison of structure,log<Emphasis Type="Italic">P</Emphasis> and P388 cytotoxicity of some phenyl and ferrocenyl cyclic chalcone analogues. Application of RP-TLC for log<Emphasis Type="Italic">P</Emphasis> determination of the ferrocenyl analogues

Cyclic chalcone analogues (2–5) and their ferrocenyl counterparts (6–10) were synthesized and their logP and P388 cyctotoxity were investigated. The structures of the newly synthesized compounds were confirmed by IR ¹H and ¹³NMR spectroscopy. Comparison of conjugation and stereochemistry of the respective derivatives showed similar characteristics compared to ones with some higher degree of conjugation in the ferrocenyl series. Comparison of logP of the ferrocenyl derivatives determined by a validated RP-TLC method showed the ferrocenyl derivatives to have higher logP _TLC. The results demonstrate that the differences in three dimensional shape, conjugation and lipophilicity do not have strong influence on the P388 cytotoxicity of the investigated phenyl (1−5) and ferrocenyl (6−10) enones.      

Synthesis of antibacterial and antifungal cobalt(II), copper(II), nickel(II) and zinc(II) complexes with bis‐(1,1′‐disubstituted ferrocenyl)thiocarbohydrazone and bis‐(1,1′‐disubstituted ferrocenyl)carbohydrazone

The condensation reaction of 1,1′‐diacetylferrocene with thiocarbohydrazide and carbohydrazide to form bis‐(1,1′‐disubstituted ferrocenyl)thiocarbohydrazone and bis‐(1,1′‐disubstituted ferrocenyl)carbohydrazone has been studied. The compounds obtained have been further used as ligands for their ligand and antimicrobial properties with cobalt(II), copper(II), nickel(II) and zinc(II) metal ions. The compounds synthesized have been characterized by physical, spectral and analytical methods and have been screened for antibacterial activity against Escherichia coli, Bacillus subtillis, Staphylococcus aureus, Pseudomonas aeruginosa and Salmonella typhi, and for antifungal activity against Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glaberata using the agar well‐diffusion method. All the compounds synthesized have shown good affinity as antibacterial and antifungal agents, which increased in most of the cases on complexation with the metal ions. Copyright © 2004 John Wiley & Sons, Ltd.     

A vic -dioxime ligand bearing fluorescent coumarin moieties and its complexes; preparation,spectroscopy, and electrochemistry

The synthesis of a new vic-dioxime ligand, N,N′²-dihydroxy-O ¹,O ²-bis(4-methyl-2-oxo-2H-chromen-7-yl)oxalimidamid (LH₂) (1), bearing functional coumarins and its soluble mono- {Ni(II), Cu(II), Co(II)} and dinuclear {UO₂(II)} complexes are presented. The fluorescence properties due to the 7-hydroxy-4-methylcoumarin fluorophore, which is conjugated with vic-dioxime that functions as the MN₄ core of 1 and its complexes, are also reported. The formation of coordination complexes resulted in the blue shift in excitation spectrum and fluorescence quenching of 1. Both mononuclear {(LH)₂M, M=Ni(II), Cu(II), and Co(II)} and homodinuclear {(LH)₂(UO₂)₂(OH)₂)} complexes have been obtained with metal?:?ligand ratios of 1?:?2 and 2?:?2, respectively. The characterizations of the new compounds were made by elemental analysis, ¹H-NMR, FT-IR, UV-Vis, and LCMS data. Redox behavior of 1, involving oxime and coumarin moieties, and its complexes with Ni(II), Cu(II), Co(II) and UO₂(II) were investigated by cyclic voltammetry. The comparison of the electrochemical behavior of 1 with its complexes enabled us to identify metal-, oxime- and coumarin-based signals.     

12-Membered crown ethers. Lipophilic derivatives of benzo- and naphtho-12-crown-4 and their membrane electrode properties. Crystal structures of benzo-12-crown-4 NaI and KI complexes

Lipophilic derivatives of benzo-12-crown-4 and naphtho-12-crown-4 have been synthesized. The behavior of the parent compounds and their derivatives in membrane ion-selective electrodes have been studied. Selectivity changes have been observed with the rise in lipophilicity. Crystal structures of the NaI and KI complexes of benzo-12-crown-4 (1 and2) have been determined by X-ray analysis. The alkali metal and iodide ions are in direct contact in2 but not in1. Compound1 [Na(benzo-12-crown-4)₂]·I is triclinic, witha=13.368(8),b=10.727(7),c=10.325(4) Å; =73.56(4),=77.73(4), =108.70(5)°;Z=2, space group is . Compound2 [K(benzo-12-crown-4)₂·I] is monoclinic, witha=15.807(8),b=12.043(4),c=15.601(6) Å,=117.74(3)°;Z=4, space groupC2/c. In both compounds the cations interact with all oxygen atoms of two crown ether molecules. Correlation of the crystal structures and behavior of the crown ethers in ion-selective membrane electrodes is discussed. Supplementary Data related to this article have been deposited with the British Library as Supplementary Publication No. 82185 (15 pages).     

Antibacterial and antifungal properties of crude extracts and isolated compounds from Lychnophora markgravii

Abstract

Antimicrobial activity of dichloromethane and ethanol extracts and five compounds: pinostrobin (I), pinocembrin (II), tectochrysin (III), galangin 3-methyl ether (IV) and tiliroside (V) isolated from Lychnophora markgravii aerial parts against fifteen microorganisms was determined. The structures of these compounds were elucidated based on ESI-MS and NMR spectroscopic data. Both extracts showed antimicrobial activity against several tested microorganisms. Pinostrobin, tectochrysin and galangin 3-methyl ether showed the strongest antibacterial and antifungal effects.     

Synthesis,Crystal Stuctures,and Properties of Two 1D Cadmium(II) Coordination Polymers Based on Ferrocenylcarboxylate

Self-assemblies of the flexible ferrocenyl block 2-chloro-4-ferrocenylbenzoate with Cd²⁺ cations in the presence of N-containing auxiliary ligand result in two coordination complexes, namely, &{[Cd(η² -OOCClH₃C₆Fc)₂(Mbbz)(CH₃OH)] · (H₂O)0.5} _n (I) and [Cd(η² -OOCClH₃C₆Fc)₂(Bbbm)] _n (II) {Fc = (η⁵- C₅H₄)Fe(η⁵-C₅H₄), Mbbz = 1,1'-methyl benzimidazole, Bbbm = 1,4-bis(benzimidazol-1-ylmethyl)-benzene}. Their structure has been determined by single-crystal X-ray diffraction analyses (CIF files nos. 1529095 (I), 1529096 (II)) and further characterized by elemental analyses, IR spectra, and thermogravimetric analyses. Crystallographic characterization shows that both I and II are 1D chain structures. Notably, various C–H···π interactions and C–H···Cl interactions are discovered in I and II, and they have significant contributions to self-assembly, which extend 1D complex to infinite 3D supramolecular networks. Moreover, the electrochemical studies of I and II in DMF solution display irreversible redox waves and indicate that the half-wave potentials of the ferrocenyl moieties in I and II are shifted to positive potential compared with that of free 2-chloro-4-ferrocenylbenzoate.     

Structures and packing of ferrocenylmethyl methacrylate and ferrocene‐1,1′‐diylbis(methylene) dimethacrylate

Electroactive metallocene polymers are of interest due to the possibility that they offer a muscle‐like response, and in gel systems very large volume changes are possible. The ferrocenyl moiety exhibits physical and electrochemical stability of the neutral and oxidized forms and could be a candidate for use as the redox‐active group in these materials. The title compounds, [Fe(C₅H₅)(C₁₀H₁₁O₂)], (I), and [Fe(C₁₀H₁₁O₂)₂], (II), comprise a typical ferrocene core with coplanar and approximately eclipsed cyclopentadienyl (Cp) rings. In (I), there is a single methyl methacrylate substituent, with the other Cp ring unsubstituted. In (II), a methyl methacrylate substituent on each Cp ring completes the structure. In both compounds, there is an s‐trans geometry of the vinyl and carbonyl components of the methacrylate group. Inversion dimers formed through C—H...O contacts dominate the crystal packing of both molecules. Weak C—H...π(ring) contacts and, in the case of (I), an unusual C—H...π(alkene) contact further stabilize the structures.     

Molecular structure and electrochemistry of carbon-bridged diferrocenyl compounds

Four diferrocenyl compounds: FcC(CH₃)₂Fc (1), Fc(CH₃)C(C₂H₅)Fc (2), Fc(CH₃)C(C₃H₇)Fc (3), and Fc(CH₃)C(C₆H₅)Fc (4) were synthesized and characterized by NMR, FT-IR, MS, and elemental analysis. The molecular structures were determined by using X-ray single crystal diffraction. The electrochemical interactions between two ferrocenyl units in these compounds were investigated by cyclic voltammetry and theoretical calculation. The electron density of bridging carbon was a key factor for the separation of two ferrocenyl units.