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

Kocak, F. Sanem
Kavakli, Cuneyt
Akyol, Ceyhun
Önal, Ahmet Muhtar
Özkar, Saim
Thermal substitution reaction of Cr(CO)4(η2:2-1,5-cyclooctadiene), Mo(CO)4(η2:2-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.


Synthesis of ferrocenyl pyrazoles by the reaction of (2-formyl-1-chlorovinyl)ferrocene with hydrazines
Zora, Metin (Elsevier BV, 2007-10-15)
Synthesis of ferrocenyl-substituted pyrazoles via the reaction between (2-formyl-1-chlorovinyl)ferrocene and hydrazine derivatives is described. Depending upon the substitution pattern of hydrazine, the reaction affords 1-alkyl/aryl-5-ferrocenylpyrazoles and/or 1-alkyl/ aryl-3-ferrocenylpyrazoles. The reaction appears to be general for a variety of hydrazine derivatives.
Synthesis and structural characterization of a novel seven-coordinate cobalt(II) complex: 2,9-Bis(ethanolamine)-1,10-phenanthrolinechlorocobalt(II) chloride
BAYSAL, AKIN; AYDEMİR, MURAT; DURAP, FEYYAZ; Özkar, Saim; Yildirim, Leyla Tatar (Elsevier BV, 2011-05-31)
Condensation reaction of 2,9-dicarboxaldehyde-1,10-phenanthroline with 2-aminoethanol followed by NaBH4 reduction yielded the polydentate Schiff base ligand 2,9-bis(ethanolamine)-1,10-phenanthroline in its reduced form. This ligand was characterized by elemental analysis, LC-MS, IR, UV-Vis and NMR spectroscopy. Reaction of the reduced Schiff base ligand with aqueous solution of cobalt(II) chloride affords 2,9-bis(ethanolamine)-1,10-phenanthrolinechlorocobalt(II) chloride in high yield. Single crystals of th...
Synthesis and characterization of the [Ni6Ge13(CO)(5)](4-) and [Ge9Ni2(PPh3)](2-) Zintl ion clusters
Nalbant Esentürk, Emren; Eichhorn, B (Elsevier BV, 2006-01-23)
Reactions between K4Ge9, Ni(CO)(2)(PPh3)(2), and 2,2,2-crypt in ethylenediamine solutions give two different products depending on reaction conditions. The [Ni6Ge13(CO)(5)](4-) ion (1) is formed at low temperatures (similar to 40 degrees C) and short reaction times whereas the [Ge9Ni2(PPh3)](2-) ion (2) forms at higher temperatures (similar to 118 degrees C). Both complexes were isolated as [K(2,2,2-crypt)](+) salts and characterized by single-crystal X-ray diffraction, electrospray mass spectrometry (ESI-M...
Synthesis of ferrocenyl pyrazoles by the reaction of 3-ferrocenylpropynal with hydrazinium salts
Zora, Metin; Odabasoglu, Mustafa; Bueyuekguengoer, Orhan; Turgut, Guenseli (Elsevier BV, 2008-01-01)
Synthesis of ferrocenyl-substituted pyrazoles via the reaction between 3-ferrocenylpropynal and hydrazinium salts is described. Depending upon the substitution pattern of hydrazine derivative, the reaction affords 1-alkyl/aryl-5-ferrocenylpyrazoles and/or 1-alkyl/aryl-3-ferrocenylpyrazoles. Structures of 5-ferrocenyl-1-phenyl-1H-pyrazole, 1-benzyl-5-ferrocenyl-1H-pyrazole and 2-(3-ferrocenylpyrazol-1-yl)ethanol were identified by X-ray crystallography.
Synthesis and characterizations of N,N,N ',N '-tetrakis (diphenylphosphino)ethylendiamine derivatives: Use of palladium(II) complex as pre-catalyst in Suzuki coupling and Heck reactions
AKBA, OSMAN; DURAP, FEYYAZ; AYDEMİR, MURAT; BAYSAL, AKIN; Guemguem, Bahattin; Özkar, Saim (Elsevier BV, 2009-03-01)
Oxidation of N,N,N',N'-tetrakis(diphenylphosphino)ethylendiamine (1) with elemental sulfur and selenium gives the corresponding sulfide and selenide, respectively, [(Ph2P(E))(2)NCH2CH2N(P(E)Ph-2)(2)] (E: S 1a, Se 1b). Complexes of 1 [(M2Cl4){(Ph2P)(2)NCH2CH2N(PPh2)(2)}] (M: Ni(II) 1c, Pd(II) 1d, Pt(II) 1e) were prepared by the reaction of 1 with NiCl2 or [MCl2(COD)] (M = Pd, Pt). The new compounds were characterized by NMR, IR spectroscopy and elemental analysis. The catalytic activity of Pd(II) complex 1d ...
Citation Formats
F. S. Kocak, C. Kavakli, C. Akyol, A. M. Önal, and S. Özkar, “Synthesis and electrochemistry of Group 6 tetracarbonyl (N,N ’-bis(ferrocenylmethylene)ethylenediamine)metal(0) complexes,” JOURNAL OF ORGANOMETALLIC CHEMISTRY, pp. 5030–5037, 2006, Accessed: 00, 2020. [Online]. Available: