Synthesis and structural characterization of new multiferrocenyl diyne ligands and their cobalt carbonyl complexes

New multiferrocenyl diyne ligands FcC(CH₃)₂Fc′–C≡C–C≡C–Fc [L ₁ ; Fc?=?C₅H₅FeC₅H₄; Fc′?=?C₅H₅Fe(1,3-disubstituted)C₅H₃], FcC(CH₃)₂Fc′–C≡C–C≡C–Fc′C(CH₃)₂Fc (L ₂ ) and their complexes [FcC(CH₃)₂Fc′–C≡C–C≡C–Fc][Co₂(CO)₆] _n [n?=?1, (1); n?=?2, (2)], [FcC(CH₃)₂Fc′–C≡C–C≡C–Fc′C(CH₃)₂Fc][Co₂(CO)₆] _n [n?=?1, (3); n?=?2, (4)] have been synthesized by the coupling reaction of terminal ferrocenylacetylene and the reaction of ligands L₁ and L₂ with Co₂(CO)₈. The composition and molecular structure of the ligands L₁ , L₂ and their cobalt complexes were characterized by element analysis, IR, ¹H(¹³C)NMR and MS. The electrochemical properties of compounds L₁ , L₂ , 1, 2, 3, 4 were studied by cyclic voltammetry(CV). The results of the electrochemical research reveal that all three ferrocenyl groups in L₁ become redox active centers, but there are only two (not four) ferrocenyl redox active centers in L₂ .     

Synthesis,molecular structure and reactivity of new biferrocenylpropane derivatives

New biferrocenylpropane derivatives FcC(CH₃)₂Fc′-C≡C–R [Fc?=?C₅H₅FeC₅H₄; Fc′?=?C₅H₅FeC₅H₃, R?=?C₆H₅ (L ₁ ), Fc (L ₂ )] and their complexes [FcC(CH₃)₂Fc′-C≡C–R][Co₂(CO)₆] [R?=?C₆H₅ (1); R?=?Fc (2)] have been synthesized by the Castro-Stephens coupling reaction and the reactions of ligands L ₁ , L ₂ with Co₂(CO)₈. Compounds L ₁ , L ₂ , 1 and 2 were characterized by elemental analysis, IR, ¹H (¹³C) NMR and MS, and the molecular structures of ligands L ₁ , L ₂ were determined by X-ray single crystal analysis. The electrochemical properties of L ₁ , L ₂ , 1 and 2 demonstrate two or three resolved one-electron redox processes.     

Synthesis and structural characterization of ferrocenyl indenyl derivatives

In this study, four ferrocenyl indenyl derivatives, C₉H₇–C≡C–Fc (1), C₉H₇–C≡C–Ph–Fc (2), C₉H₇–C≡C–Ph–C≡C–Fc (3), and C₉H₇–Ph–C≡C–Fc (4) (where C₉H₇=indenyl; Fc=C₅H₅FeC₅H₄; Ph=C₆H₅), have been synthesized by Sonogashira and Suzuki cross-coupling reactions and characterized by elemental analysis, and FT-IR, ¹H, ¹³C-NMR, and MS spectroscopic methods, respectively. The molecular structures of 1, 2, and 4 were determined by X-ray single crystal diffraction. Two molecules appeared in the crystal structure of 4, and they interact through an intermolecular hydrogen bond. The electrochemical redox potential differences in 1–4 were investigated using cyclic voltammetry and calculations.     

Syntheses,spectroscopic characterizations and crystal structures of diorganotin(IV)-oxo-carboxylates with 2-pyrazinecarboxylic acid or (2-pyrimidylthio)acetic acid

Eight diorganotin(IV)-oxo-carboxylates {[R₂Sn(O(O)CR′)]₂O}₂?·?Y (R′?=?C₄H₃N₂Y?= H₂OR?=?ⁿBu 1, Y?=?0 R?=?Me 2, Y?=?0 R?=?C₆H₅ 3, Y?=?0 R?=?C₆H₅CH₂ 4; R′?=?CH₂SC₄H₃N₂-2,6Y?=?0 R?=?ⁿBu 5, Y?=?CH₂Cl₂R?=?Me 6, Y?=?0 R?=?C₆H₅ 7, Y?=?0 R?= C₆H₅CH₂ 8) have been prepared in 1?:?1 molar ratios by reactions of diorganotin(IV) oxide with 2-pyrazinecarboxylic acid or (2-pyrimidylthio)acetic acid, respectively. All the complexes are characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectra. Except for 2, 4 and 7, the complexes are also characterized by X-ray crystallography diffraction analyses, which reveal that the complexes adopt the familiar dicarboxylato tetraorganodistannoxane structural mode. Among them, the evident difference is that weak intramolecular interactions between Sn and N atoms are recognized in complexes 1 and 3. However, for complex 5 two different coordination modes are found in the same lattice.     

Construction of Zn(II)-ferrocenyl carboxylate coordination complexes via changing adjuvant ligands

Five Zn(II)-ferrocenyl carboxylate complexes, {[Zn(OOCClH₃C₆Fc)(η ²OOCClH₃C₆Fc)(dpa)]?·?(H₂O)} (1), [Zn(η ²-OOCClH₃C₆Fc)₂(2,2′-dip)]?·?(H₂O)_0.25} (2), {[Zn(η-OOCClH₃C₆Fc)₂(bix)]₂?·?(THF)} (3), [Zn(η-OOCClH₃C₆Fc)₂?·?(Hfcz)] _n (4) and {[Zn(η-OOCClH₃C₆Fc)₂(H₂L₁)]?·?(DMF)₂} _n (5) [dpa?=?2,2′-dipyridylamine, 2,2′-dip?=?2,2′-bipyridine, bix?=?1,4-bis(imidazol-1-ylmethyl)benzene, Hfcz?=?α-(2,4-difluorophenyl)-α-(1H-1,2,4-triazol-l-ylmethyl)-1H-1,2,4-triazole-l-ethanol, H₂L₁?=?N,N′-bis(pyridin-4-yl)pyridine-2,6-dicarboxamide, Fc?=?ferrocene, FcC₆H₃ClCOONa?=?sodium 2-chloro-4-ferrocenylbenzoic], have been synthesized and characterized. Single-crystal X-ray analysis reveals that 1 and 2 are mononuclear structures, 3 is a dimer, and 4 and 5 are 1-D structures. The five complexes exhibit some differences in their conformations, which can be attributed to the influence of adjuvant ligands. Notably, various π–π interactions as well as CH/π interactions are discovered in 1–5, and they have significant contributions to self-assembly. The electrochemical properties of 1–5 indicate that half-wave potentials shift to positive potential compared with that of 2-chloro-4-ferrocenylbenzoic acid.     

Synthesis and Characterizations of Ferrocenyl Carbonyl Chromium and Cobalt Clusters

Two novel bimetallic complexes, [Cr(CO)₃(η ⁶-C₆H₅)–C≡C–C₆H₄–Fc] (Fc = C₅H₅FeC₅H₄] (1) and [Cr(CO)₃(η ⁶-C₆H₅)–C ≡ C–Fc–C(CH₃)₂–Fc] (3), were synthesized by the Sonogashira coupling reaction. By using of (1) and (3) as ligands to react with Co₂(CO)₈, two others novel polymetallic complexes, [Cr(CO)₃(η ⁶-C₆H₅){Co₂(CO)₆-η ²-μ ²-C≡C–}–C₆H₄–Fc] (2) and [Cr(CO)₃(η ⁶-C₆H₅){Co₂(CO)₆-η ²-μ ²-C≡C–}Fc–C(CH₃)₂–Fc] (4) were obtained. Four carbonyl complexes were characterized by elemental analysis, FT-IR, NMR and MS. The molecular structures of complexes (1), (2) and (4) were determined by single crystal X-ray diffraction. The interactions among the ferrocenyl, Cr(CO)₃ and Co₂(CO)₆-η ²-μ ²-C≡C– units were investigated by cyclic voltammetry.     

Thermotropic liquid crystals based on ferrocenylbiphenyl and ferrocenylterphenyl

4′‐Ferrocenyl‐1,1′‐biphenyl‐4‐yl 4‐alkoxybenzoates Fc–(C₆H₄)₂–OC(O)–C₆H₄–O–C _n H_2n+1 (n = 8, 10, 12) (3a–c), representing a new class of ferrocene‐containing thermotropic mesogens with nematogenic properties, were prepared. Two approaches were used for the construction of these mesogens: (i) reaction of 4′‐ferrocenyl‐1,1′‐biphenyl‐4‐ol with 4‐alkoxybenzoylchlorides, and (ii) crosscoupling of tris(4‐ferrocenylphenyl)boroxine with the corresponding halobenzenes. Crosscoupling was also applied for the synthesis of terphenyl‐containing mesogens Fc–(C₆H₄)₃–OC(O)–C₆H₄–O–C _n H_2n+1 (n = 10, 12) (6a,b) and (RC₅H₄)Fe‐[C₅H₄–(C₆H₄)₃–OC(O)–C₆H₄–O–C₁₀H₂₁] (11a, R = Et; 11b, R = n?Bu). The latter compounds also form nematic phases. Mesogens 6a,b form mesophases with wider temperature ranges than their biphenyl‐containing counterparts 3b,c. The most pronounced mesomorphism was displayed by compounds 11a and 11b, which have mesophases in the ranges 141–253°C and 120–238°C, respectively. The purity of compounds was established by ¹H NMR spectra and elemental analysis. Mesophases were identified by polarizing optical microscopy and differential scanning calorimetry.     

Darstellung von Ferrocenyltriethylstannanen sowie elektronische Eigenschaften der substituierten Ferrocenylliganden

Synthesis of Ferrocenyltriethylstannanes and Electronic Properties of Substituted Ferrocenyl Ligands Ferrocenyltriethylstannanes of the type RSnEt₃ [R = Et₃SnC₅H₄FeC₅H₄, C₅H₅FeC₅H₃(2-CH₂NMe₂), C₅H₅FeC₅H₃(2-CH₂NC₅H₁₀), C₅H₅FeC₅H₃(2-CH₂OMe), MeOCH₂C₅H₄FeC₅H₄] were synthesized from Et₃SnCl and the corresponding ferrocenyl lithium derivatives. The compounds were characterized by elementary analyses, ¹H-, ¹³C-, ¹¹⁹Sn-n.m.r. and i.r. spectroscopic investigations. From the coupling constants ¹J(¹¹⁹Sn? ¹³C_Et) the electronic influence of substituted ferrocenyl ligands was estimated.     

1-烷基-1'-乙酰基二茂铁的合成

用新方法合成了1-烷基-1'-乙酰基二茂铁, 该法与传统方法相比易于得到单一产物. 通过7种1-烷基二茂铁甲酸与三氯化磷作用形成酰氯, 再与乙酰乙酸乙酯的钠盐进行反应, 皂化脱羧得到1-烷基-1'-乙酰基二茂铁化合物, 用元素分析、红外光谱、核磁共振氢谱确定了化合物的结构.     

Syntheses and structural characterization of organotin(IV) complexes derived from reaction of 2,3-diphenylpropionic acid and various alkyltin salts

Five new organotin(IV) complexes, [(R₃Sn)(O₂C₁₅H₁₃)] _n (R?=?Me: 1; nBu: 2), [RSn(O)(O₂C₁₅H₁₃)]₆ (R?=?Ph: 3), [(R₂Sn)₂(O₂C₁₅H₁₃)₂(μ ₃-O)]₂ (R?=?Me: 4), and [(R₂Sn)(O₂C₁₅H₁₃)₂] (R?=?nBu: 5), have been prepared by the reaction of 2,3-diphenylpropionic acid and the corresponding organotin chloride with sodium ethoxide in methanol. All the complexes were characterized by elemental analysis, FT-IR, NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopy, TGA, and X-ray crystallography. The structural analyses reveal that 1 and 2 are 1-D infinite polymeric chains with Sn in syn–anti conformation. Complex 3 has a drum structure with six Sn centers. Complex 4 has a supramolecular chain-like ladder through weak intermolecular Sn?···?O interactions. Complex 5 is a monomer, connected into a 1-D polymer through intermolecular C–H?···?O interactions. Complexes 1 and 5 crystallize in the orthorhombic space groups P212121 and P21212, which are chiral space groups.     

Tetrahedral manganese(II) complexes of 1-alkyl-2-(arylazo)imidazoles. X-ray crystal structure of [Mn(HaaiMe)4](ClO4)2·DMF (HaaiMe = 1-methyl-2-(phenylazo)imidazole)

[Mn(RaaiR′)₄](ClO₄)₂ complexes have been synthesised by reacting Mn(ClO₄)₂·6H₂O and RaaiR′ in methanol (RaaiR′?=?1-alkyl-2-arylazo)imidazole, R?=?H (a), Me (b), Cl (c); R′?=?Me (1), Et (2)). The orange–red crystalline compounds were characterised by microanalytical, spectroscopic, magnetic, thermal and electrochemical data. A single-crystal X-ray diffraction study of a DMF adduct of 1a revealed tetrahedral orientation of four ligands coordinating through imidazole-N while the azophenyl group (–N=N–Ph) is pendant. Cyclic voltammetry shows the Mn(III)/Mn(II) couple at >?1.0?V along with azo reductions.     

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.     

Cadmium(II) complexes with phosphine tellurides: synthesis and multinuclear (31P, 125Te,and 113Cd) NMR characterization in solution

New cadmium(II) complexes with phosphine telluride ligands of the type CdX₂(R₃PTe)_n [X?=?ClO₄^?, n?=?4: R?=?n-Bu (1), Me₂?N (2), C₅H₁₀?N (3), C₄H₈?N (4) or OC₄H₈?N (5); X?=?Cl^–, n?=?2: R?=?n-Bu (6), Me₂?N (7), C₅H₁₀?N (8), C₄H₈?N (9) or OC₄H₈?N (10)] have been synthesized and characterized by elemental analyses, IR and multinuclear (³¹P, ¹²⁵Te, and ¹¹³Cd) NMR spectroscopy. In particular, the solution structures of these complexes were confirmed by ¹¹³Cd NMR at low temperature, which displays a quintuplet for each of the perchlorate complexes and a triplet for each of the chloride complexes due to coupling with four and two equivalent phosphorus atoms, respectively, indicating a four-coordinate tetrahedral geometry for the metal center. These multiplet features were further accompanied by one bond Te–Cd couplings, clearly showing that the ligand is coordinated to the metal through tellurium. The results are discussed and compared with those obtained for closely related phosphine chalcogenide analogs.     

Ferrocene-carboxylate coordination complexes bridged by different N-containing ligands

Six new coordination complexes, [Cd(η ²-OOCCH=(CH₃)CFc)₂(bix)]₂·(CH₃OH)_0.5 (1), [Zn(η ²-OOCCH=(CH₃)CFc)(η ¹-OOCCH=(CH₃)CFc)(bix)]₂·(H₂O)_0.5 (2), [Zn(η ²-OOCCH=(CH₃)CFc)₂(pbbm)]₂·(CH₃OH)₂ (3), {[Mn(η ¹-OOCCH=(CH₃)CFc)₂(bbbm)(H₂O)₂]·(CH₃OH)₃}_n (4), {[Cd(η ¹-OOCCH=(CH₃)CFc)₂(bbbm)]·(CH₃OH)₂}_n (5), and [Cd(η ²-OOCCH=(CH₃)CFc)₂(pmbbm)]_n (6) {Fc?=?(η ⁵-C₅H₄)Fe(η ⁵-C₅H₄), bix?=?1,4[bis(imidazol-1-ylmethyl)benzene], pbbm?=?1,1′-[(1,4-propanediyl)bis-1H-benzimidazole], bbbm?=?1,1′-[(1,4-butanediyl)bis-1H-benzimidazole)], pmbbm?=?1,1′-[(1,4-pentanediyl)bis-1H-benzimidazole]}, were prepared and characterized. X-ray crystallographic analysis reveals that 1–3 are dimers bridged by bix and pbbm. Complexes 4–6 are one-dimensional (1-D) structures bridged by bbbm and pmbbm, respectively. Various π–π interactions were discovered in 1–6 that make significant contributions to molecular self-assembly. Solution differential pulse voltammetry of 1–6 indicates that the half-wave potentials of the ferrocenyl moieties in these complexes shift to positive potential compared with that of 3-ferrocenyl-2-crotonic acid.     

Complexes based on ferrocenecarboxylate ligands: steric hindrance induced by ferrocenyl groups

Three metal complexes with ferrocenecarboxylate ligands, [M₂(η ²-FcCOO)₂(μ₂-η ²-FcCONHCH₂COO)₂(phen)₂]?·?nH₂O [M?=?Pb, n?=?6 (1) and M?=?Cd, n?=?2 (2)] and [Cd(FcCONHCH₂COO)(μ₂-FcCONHCH₂COO)(2,2′-bipy)(H₂O)] _n (3) (FcCOOH?=?ferrocenemonocarboxylic acid, FcCONHCH₂COOH?=?N-ferrocenylformylglycine, phen?=?1,10-phenanthroline, 2,2′-biby?=?2,2′-bipyridine), were synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction analysis. Structural studies revealed that 1 and 2 have similar binuclear structures, but 3 exhibits a 1-D chain structure. The difference in the structures of ferrocenylcarboxylate-containing cadmium(II) complexes is due to steric hindrance of ferrocenyl groups.     

Syntheses and characterization of four coordination compounds derived from 10,11,12,13-tetrahydro-4,5,9,14-tetraaza-benzo[b]triphenylene and benzene-dicarboxylic acids

[Co₂(TTBT)₄(1,2-BDC)₂] _n ?·?4nH₂O (1), [Pb₂(TTBT)₂(1,3-BDC)₂] _n ?·?nTTBT?·?2nH₂O (2), [Fe(TTBT)(1,4-BDC)(H₂O)] _n (3), and [Zn(TTBT)(1,4-BDC)(H₂O)] _n (4) have been hydrothermally synthesized by self-assembly of TTBT (TTBT?=?10,11,12,13-tetrahydro-4,5,9,14-tetraaza-benzo[b]triphenylene), benzene-dicarboxylic acid ligands 1,2-H₂BDC, 1,3-H₂BDC or 1,4-H₂BDC (1,2-H₂BDC?=?1,2-benzenedicarboxylic acid, 1,3-H₂BDC?=?1,3-benzenedicarboxylic acid, 1,4-H₂BDC?=?1,4-benzenedicarboxylic acid), and various metal salts. Compound 1 has dinuclear cluster units, four dimeric Co₂ units connected to form a 32-membered ring via weak offset π–π interactions, which are further stacked via strong π–π interactions to form a 3-D supramolecular framework. Complex 2 contains 2-D layers with rhombohedral grids, which are connected to a 3-D structure by π–π interactions. 3 and 4 feature 1-D infinite chains, which are further extended by strong π–π interactions and O–H···O hydrogen bonds resulting in 3-D supramolecular architectures. The photoluminescent properties of 2 and 4 have also been investigated.     

Synthesis,characterization, and antibacterial activity of organotin(IV) complexes with 2-hydroxyacetophenone thiocarbohydrazone

Six new organotin(IV) complexes were synthesized by direct reaction of RSnCl₃ (R?=?Me, Bu and Ph) or R₂SnCl₂ (R?=?Me, Bu and Ph) and 2-hydroxyacetophenone thiocarbohydrazone [H₂APTC] under purified nitrogen in the presence of base in 1?:?2?:?1 molar ratio (metal: base: ligand). Complexes 2–7 have been characterized by elemental analyses, molar conductivity, UV-Visible, IR and ¹H NMR spectral studies. Complexes 2–7 are non-electrolytes. The molecular structure of [Me₂Sn(APTC)]?·?(C₂H₅OH) (5) has been determined by X-ray diffraction analysis. The thiocarbohydrazone ligand (1) and 2–7 have been tested for antibacterial activity against Escherichia coli, Staphylococcus aureus, Salmonella typhi and Enterococci aeruginosa.     

Coordination polymers of lanthanides incorporating N,N′-ethylenebis(2-hydroxy-1-naphthylideneiminato): syntheses and crystal structures

Reaction of Ln(NO₃)₃?·?6H₂O with H₂napn (H₂napn?=?N,N′-ethylenebis(2-hydroxy-1-naphthylideneiminato)) and KSCN produces seven new coordination polymers, [La(H₂napn)(SCN)(C₂H₅OH)₂(NO₃)₂] _n (1), [La(H₂napn)₂(SCN)(NO₃)₂] _n (2), and [Ln(H₂napn)_1.5(NO₃)₃] _n [Ln?=?La(3), Sm(4), Eu(5), Dy(6), Er(7)]. Crystal structure analysis reveals that H₂napn functions as a bridging ligand, forming a 1-D chain polymer (1) and 2-D open-frameworks (2–7) with lanthanides. Each metal center of 1–7 is nine-coordinate. Lanthanide contraction is observed in 3–7.     

A three‐dimensional twofold interpenetrated cobalt(II) MOF containing a flexible carboxylate‐based ligand: synthesis,structure and magnetic properties

The design and synthesis of coordination polymers (CPs) have attracted much interest due to the intriguing diversity of their architectures and topologies. The functional solid catena‐poly[μ₂‐aqua‐triaqua{μ₄‐5‐[4‐carboxyphenoxy)methyl]benzene‐1,3‐dicarboxylato}{μ₃‐5‐[4‐carboxyphenoxy)methyl]benzene‐1,3‐dicarboxylato}dicobalt(II)], [Co₂(C₁₆H₁₀O₇)₂(H₂O)₄]_n or [Co₂(HL)₂(μ₂‐H₂O)(H₂O)₃]_n, was synthesized successfully by self‐assembly of Co^II ions with 5‐[(4‐carboxyphenoxy)methyl]isophthalic acid (H₃L). The title compound was obtained under hydrothermal conditions and exhibits a twofold interpenetrated three‐dimensional skeleton with hms 3,5‐conn topology according to the cluster representation for valence‐bonded metal–organic frameworks (MOFs). It has been characterized by single‐crystal X‐ray diffraction, IR spectroscopy, powder X‐ray diffraction (PXRD), thermogravimetric analysis and susceptibility measurements. The antiferromagnetic coupling between adjacent Co^II centres occurs via superexchange through the ligands.     

Transition metal derivatives of 1,1′-dichloroferrocene

Complexes of the general formula [Cl₂Fc] _nML, (Cl₂Fc = C1C₅H₄FeC₅H₃Cl; ML = Fe(CO)₂C₅H₅, AuP(C₆H₅)₃, Mn(CO)₅ or Ir(CO)[P(C₆H₅)₃]₂ when n = 1; ML = Ti(C₅H₅)₂ when n = 2) have been prepared from a salt elimination reaction between 1,1′-dichloro-2-lithioferrocene and transition metal halide complexes. Spectroscopic properties of the compounds are reported. The titanium complex exists in meso and dl forms.