Synthesis and electrochemistry of Group 6 tetracarbonyl (N,N′-bis(ferrocenylmethylene)ethylenediamine)metal(0) complexes

Thermal substitution reaction of Cr(CO)₄(η^2:2-1,5-cyclooctadiene), Mo(CO)₄(η^2:2-norbornadiene), and W(CO)₅(η²-bis(trimethylsilyl)ethyne) with N,N′-bis(ferrocenylmethylene)ethylenediamine (bfeda) yields M(CO)₄(bfeda) complexes which could be isolated from the reaction solution and characterized by elemental analysis, MS, IR, and NMR spectroscopy. In the case of tungsten, W(CO)₅(bfeda) is formed as intermediate and then undergoes the ring closure reaction yielding the ultimate product W(CO)₄(bfeda). The electrochemical behavior of the M(CO)₄(bfeda) complexes was studied by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in dichloromethane with tetrabutylammonium tetrafluoroborate as electrolyte. Constant potential electrolysis of the complexes was performed successively at their peak potentials at 0 °C in their CH₂Cl₂ solution and the electrolysis was followed by in situ recording the electronic absorption spectra in every 5 mC. In the electrolysis of Cr(CO)₄(bfeda), the central Cr(0) is oxidized first and electrolysis continues with oxidations of two ferrocenyl groups until the end of totally three moles of electron passage per mole of complex. In the electrolysis of Mo(CO)₄(bfeda) and W(CO)₄(bfeda) the first oxidation occurs on the central atom forming a short-lived species which undergoes an intramolecular one-electron transfer and is reduced back to M(0) while one of the ferrocene units is oxidized to the ferrocenium cation at the same time. This indicates that the electron is transferred from iron to the central metal atom.     

Formation of the paramagletic Ni(I) π-allyl complex in the Ni(allyl)2 - (2,6-diisopropylphenyl)diazabutadiene system

It has been shown that the reaction of Ni(allyl)₂ with (2,6-diisopropylphenyl)diazabutadiene gives the imino-amide Ni complex (1). The imino-amide moiety of this complex undergoes some complicated rearrangements resulting in spontaneous formation of a paramagnetic π-allyl Ni(I) complex. Nickel complexes formed in the system have been studied with ESR, FTIR, 2D NMR, and mass spectrometry. The structure of complex 1 was studied with X-ray diffraction.     

Copper(I)-1,1,1-tris(diphenylphosphinomethyl)ethane complexes with different coordination modes tuned by auxiliary ligands and their spectroscopic properties

Three mono-, bi- and tetranuclear copper(I) complexes, [Cu(phen)(triphos-O)]BF₄ (1) (phen = 1,10-phenanthroline, triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane), [Cu₂(bipy)(triphos)₂](BF₄)₂ (2) (bipy = 4,4′-bipyridine), and [Cu₄(MeOC^N^N)₄(triphos)₂(bipy)](BF₄)₄ (3) (MeOC^N^N = 6-(4-methoxyphenyl)-2,2′-bipyridine), have been synthesized and characterized by NMR spectroscopy, electrospray ionization, and matrix-assisted laser desorption ionization time-of-flight mass spectrometries, elemental analysis, and X-ray crystal analysis. The crystal structure investigation revealed the copper ions of the complexes have pseudo-tetrahedral coordination geometry. The electronic absorption spectra of 1, 2, and 3 contain low-energy bands at 350–500 and 400–650 nm, which are assigned to d(Cu) → π*(phen or bipy) and a mixture of d(Cu) → π*(MeOC^N^N) and d(Cu) → π*(bipy) transitions, respectively. Complex 2 displays a strong, long-lived solid-state emission with a maximum at 555 nm and lifetime of 13.6 μs at room temperature. Photoinduced electron-transfer properties of 2 and 3 involving nanosecond time-resolved absorption spectroscopy and electron spin resonance techniques were studied.     

一种新型双亚胺吡啶铁系催化剂的乙烯低聚研究

线性α 烯烃广泛地应用于洗涤剂、增塑剂、润滑油等精细化学品的合成以及作为共单体制备线性低密度聚乙烯 (ＬＬＤＰＥ) .目前工业上主要是应用ＳＨＯＰ法[1] 、Ｃｈｅｖｒｏｎ工艺和Ａｍｏｃｏ工艺[2 ] 通过乙烯低聚制备 .近些年发展起来的新型高活性后过渡金属乙烯低聚催化剂能够高选择性地制备线性α 烯烃[3 ,4] .Ｂｒｏｏｋｈａｒｔ等[4] 的研究表明 ,对于双亚胺吡啶铁系乙烯聚合催化剂而言 ,配体上苯基的邻位取代基位阻减小可以实现乙烯低聚 ,并具有高活性、高选择性以及理想的低聚产物分布 .本文的工作是从配体的空间位阻效应对催化剂…     

Ruthenium (II) polypyridyl complexes based on bipyridine and two novel diimine ligands with carrier-transporting unit: synthesis, photoluminescence and redox properties

A series of ruthenium (II) complexes, [Ru(bpy)₂L]X₂ (L = L1, L2; X = Cl⁻, PF₆⁻, SCN⁻), were synthesized based on bipyridine and two novel diimine ligands L1 and L2 (L1 = 1-(4-5′-phenyl-1,3,4-oxadiazolylphenyl)-2-pyridinyl-benzoimidazole, L2 = 1-(4-carbazolylphenyl)-2-pyridinylbenzimidazole); and the crystal structure of [Ru(bpy)₂L1]Cl₂ was also described. [Ru(bpy)₂(Pybm)]X₂ (Pybm = 2-(2-pyridine)benzimidazole) complexes were also prepared as reference samples. In the UV-vis absorption spectra there are one strong π → π* transition and two dπ (Ru) → π* transitions. By comparisons of photoluminescence properties between [Ru(bpy)₂L]X (L = L1, L2) and the reference complexes we find that the complexes with carrier-transporting groups of carbazole and oxadizole have the higher emission intensity and quantum efficiency. One reversible oxidation process in the range 0.80-1.00 V exists in each of the complexes which is assigned to the metal oxidation, [Ru(III)(bpy)₂L]²⁺ + e⁻?[Ru(II)(bpy)₂L]⁺.     

New Re(I) tricarbonyl-diimine complexes with N,N′-bis(substituted benzaldehyde)-1,2-diiminoethane Schiff base ligands: Synthesis,spectroscopic and electrochemical studies and crystal structures

The syntheses, structures and spectroscopic properties of tricarbonylrhenium(I) complexes with N,N′-bis(2-bromo, 4-bromo, 4-chloro and 3-methoxybenzaldehyde)-1,2-diiminoethane Schiff base ligands have been investigated in this paper. Characterization of these complexes was carried out with FTIR, NMR, UV–Vis spectroscopy, elemental analysis and X-ray crystallography. The electrochemical behavior of the investigated complexes has been studied by cyclic voltammetry. The crystal structures of the 4-chloro, 4-bromo and 4-methoxy substituted complexes are stabilized by intermolecular C–H?Cl and C–H?O hydrogen bonds. The remarkable features of the 2-bromo, 4-bromo and 4-chloro substituted complexes are short intermolecular halogen–oxygen contacts. In the 4-bromo complex, short intermolecular Br?O and O?O contacts link neighboring molecules along the [1 0 0] direction, which are further stabilized by short intermolecular π?π interactions. In 2-bromo complex, intermolecular Br?O interactions link neighboring molecules into 1D extended chains along the [0 1 0] and [0 0 1] directions, forming a 2D network which is parallel to the bc-plane.     

Selectivities in the reaction of vicinal diimines and acyl chlorides

The reaction of vicinal diimines and acyl chlorides in the presence of triethylamine produces 3-imino-β-lactams and/or bis-β-lactams chemo-, regio-, and stereoselectively, which are important intermediates in pharmaceutical and organic synthesis. The selectivities in the reaction have been investigated. The results indicate that all diimines react with various ketenes generated from acyl chlorides in the presence of triethylamine to give rise to cis-4-imino-β-lactams (mono-cis-β-lactams) diastereoselectively due to the electron-withdrawing property of the imino group in the vicinal diimines. Bis-β-lactams were obtained from diimines via the mono-cis-β-lactams as intermediates. Only ketenes with strong electron-donating substituents can react with the mono-cis-β-lactams to yield bis-β-lactams, affording a pair of C2-symmetric cis-bis-β-lactams with symmetric diimines, two or four pairs of diastereomeric bis-β-lactams with ketoaldehyde-derived unsymmetric diimines depending on the steric hindrance of their N-substituents. The current investigation provides very important information for the selective preparation of mono- and bis-β-lactams from vicinal diimines.     

C‐O Bond Cleavage of Diethyl Ether and Tetrahydrofurane by [(dpp‐BIAN)AlI(Et2O)] [dpp‐BIAN = 1,2‐bis[(2,6‐di‐iso‐propylphenyl)‐imino]acenaphthene]

At elevated temperatures, the aluminum complex [(dpp‐BIAN)AlI(Et₂O)] ( 1 ) splits the C‐O bonds of diethyl ether and tetrahydrofurane yielding the dimeric alkoxides [(dpp‐BIAN)AlOEt]₂ ( 2 ) and [(dpp‐BIAN)AlO(CH₂)₄I]₂ ( 3 ), respectively. Already at ambient temperatures, a cleavage of the C‐O bond of THF is to observe in the reaction of 1 with CpNa in THF as confirmed by the formation of [(dpp‐BIAN)AlO(CH₂)₄C₅H₅]₂ ( 4a ) and [(dpp‐BIAN)Al{O(CH₂)₄C₅H₅}(THF)] ( 4b ) in a molar ratio of 1:2. The reaction of 1 with t‐BuOK affords the monomeric alkoxide [(dpp‐BIAN)AlO‐t‐Bu(Et₂O)] ( 5 ). Compounds 2 , 3 , and 4a/b were characterized by elemental analyses and IR spectra. Additionally, the structures of 2 and 3 were determined by single crystal X‐ray diffraction.     

Synthesis of tungsten compounds with Schiff base ligands prepared from ferrocenecarboxaldehyde: Observation of the migration of an imine double bond

The one-pot reactions of ferrocenecarboxaldehyde, W(CO)₄(pip)₂ (pip = piperidine) and either 2-(aminomethyl)pyridine or 2-(2-aminoethyl)pyridine lead to clean formation of pyridine imine products W(CO)₄(η²-NC₅H₄CHNCH₂C₅H₄FeCp) (1) and W(CO)₄(η²-NC₅H₄C₂H₄NCHC₅H₄FeCp) (2), respectively. Crystal structures of the two compounds show that in 1 the imine double bond has migrated so that it is conjugated with the pyridine ring while in 2 the imine double bond remains conjugated with the cyclopentadienyl ring. This finding is reinforced by a comparison of dihedral angles in each molecule. IR, NMR and electronic spectra each highlight the differences between the two compounds. Crystal data for C₂₁H₁₆FeN₂O₄W (1): monoclinic P2(1)/c, a = 12.768(2) Å, b = 13.593(2) Å, c = 12.981(2) Å, β = 119.46°, V = 1961.6(4) Å³, Z = 4; C₂₂H₁₈FeN₂O₄W (2): monoclinic P2(1)/c, a = 16.759(1) Å, b = 8.8612(7) Å, c = 13.802(1) Å, β = 95.998(1)°, V = 2038.4(3) Å³, Z = 4.     

Syntheses and Structures of Tris-(1,2-Benzosemiquinone DIimine) Complexes of Rhenium(IV)

Reactions of trans-[ReO₂(py)₄Cl] and cis-[ReO₂I(PPh₃)₂] with 2,3-diaminophenol (H₂dab-OH) and 1,2-diaminobenzene (H₂dab), respectively, in ethanol under aerobic conditions led to the corresponding isolation of [Re(sbqdi-OH)₃]Cl (1) and [Re(sbqdi)₃]I (2). Crystallographic data show that the ligand sbqdi represents the monoanionic N,N-coordinated π-radical form of the 1,2-benzosemiquinone diimine of H₂dab. The ligands in Complex 1 clearly show semiquinoid character; e.g., the two C-N and two Re-N bondlengths differ considerably. In 2, the phenyl rings display typical quinoid distortions with two localized double bonds, and the C-N bondlengths are short, approaching double bonds. Rhenium is formally in the +IV oxidation state.