Ismail Yilmaz | Sakarya University (original) (raw)
Papers by Ismail Yilmaz
... of topological analysis of electron density function derived from experimental X-ray ... MOME... more ... of topological analysis of electron density function derived from experimental X-ray ... MOMENTS OF A D0 METALLOCENE DERIVED BY ASSOCIATED PHOTOPHYSICAL AND DFT STUDY ... According to a method, based on solvatochromic shifts of absorption and emission ...
![Research paper thumbnail of ChemInform Abstract: The Orthopalladation Dinuclear [Pd(L1)(μ-OAc)]2, [Pd(L2)(μ-OAc)]2 and Mononuclear [Pd(L3)2] Complexes with [N, C, O] or [N, O] Containing Ligands: Synthesis, Spectral Characterization, Electrochemistry and Catalytic Properties](https://attachments.academia-assets.com/40431910/thumbnails/1.jpg)
](ChemInform, 2010
C, O] or [N, O] Containing Ligands: Synthesis, Spectral Characterization, Electrochemistry and Ca... more C, O] or [N, O] Containing Ligands: Synthesis, Spectral Characterization, Electrochemistry and Catalytic Properties. -(KILIC*, A.; KILINC, D.; TAS, E.; YILMAZ, I.; DURGUN, M.; OZDEMIR, I.; YASAR, S.; J. Organomet. Chem. 695 (2010) 5, 697-706; Dep. Chem., Univ. Harran, TR-63190 Sanliurfa, Turk.; Eng.) -Nuesgen 29-099
Transition Metal Chemistry, 2002
A novel (E,E)-dioxime and its mono-, di-and trinuclear complexes bearing tetradentate octyl sulfa... more A novel (E,E)-dioxime and its mono-, di-and trinuclear complexes bearing tetradentate octyl sulfanyl phenylamino substituents. Synthesis, characterization and electrochemical properties of its transition metal complexes Abstract A new vic-dioxime, 13,14-bis-(hydroxyimino)-9,12,15,18-diazadithiaoctacosane, has been synthesized from 2octylsulfanylaminobenzene and (E,E¢)-dichloroglyoxime. Mononuclear transition metal complexes of Ni II , Cu II , Co II and Fe II have been prepared and were found to have a metal-ligand ratio of 1:2. The synthesis of di-and trinuclear complexes was achieved with U IV O 2 and Cu II depending on the stoichiometry of the reactants. The complexes were characterized by elemental analysis, 1 H-n.m.r., u.v.-vis, i.r., f.a.b.-m.s. and by cyclic voltammetry.
Polyhedron, 2007
New Schiff-base copper and cobalt complexes,[Cu (L1)],[Cu (L2)] and [Co (L1)],[Co (L2)](where L1=... more New Schiff-base copper and cobalt complexes,[Cu (L1)],[Cu (L2)] and [Co (L1)],[Co (L2)](where L1= NN′-bis (3, 5-di-tert-butylsalicylaldimine)-1, 4-cyclohexane bis (methylamine) and L2= NN′-bis (3, 5-di-tert-butylsalicylaldimine)-1, 8-diamino-3, 6-...
Polyhedron, 2008
... Esref Tas a , Corresponding Author Contact Information , E-mail The Corresponding Author , Ah... more ... Esref Tas a , Corresponding Author Contact Information , E-mail The Corresponding Author , Ahmet Kilic a , Nazli Konak a and Ismail Yilmaz b , Corresponding Author Contact Information , E-mail The Corresponding Author. ...
Synthesis and Reactivity in Inorganic Metal-Organic and Nano-Metal Chemistry, 2009
... Esref Tas a , Hatice Kara b , Mustafa Durgun b , Ahmet Kilic b & Ismail Yilma... more ... Esref Tas a , Hatice Kara b , Mustafa Durgun b , Ahmet Kilic b & Ismail Yilmaz c pages 379-387. ... [ 25 26. Durmus, M., Ahsen, V., Luneau, D. and Pecaut. 2004. Synthesis and structures of morpholine substituted new vic-dioxime ligand and its Ni(II) complexes. J. Inorg. Chim. ...
Inorganica Chimica Acta, 2013
Journal of Coordination Chemistry, 2014
Journal of Organometallic Chemistry, 2014
ABSTRACT Herein we report the synthesis and characterization of a new series of synthesized mono-... more ABSTRACT Herein we report the synthesis and characterization of a new series of synthesized mono-and trinuclear cobaloxime/organocobaloximes from ketone that act as catalysts for cyclic carbonate synthesis from CO2 and epoxides under appropriate conditions (2 h, 100 degrees C and 1.6 MPa pressure). These reactions were carried out with and without co-catalyst, namely, 4-dimethylaminopyridine (DMAP), pyridine (py), triethyl amine (NEt3) or triphenyl phosphine (PPh3). In the catalytic experiments, the 4-dimethylaminopyridine (DMAP) was used as co-catalyst, since the DMAP was a more active base with higher yield compared to other Lewis bases. In addition, various factors influencing the cycloaddition reaction, such as co-catalyst, temperature, CO2 pressure and reaction time, were investigated. A dioxime ligand (LH2) (1) was obtained in two steps from 4-methylpropiophenone as ketone. Reaction of CoCl2.6H(2)O with the dioxime ligand (LH2) (1) and 4-tertbutyl pyridine afforded six-coordinate mononuclear cobaloxime or organocobaloxime (2-3) complexes. The mononuclear cobaloxime or organocobaloxime (2-3) complexes were used as precursors for building trinuclear cobaloximes or organocobaloxime (4-11) complexes. All compounds were fully characterized by H-1 and C-13 NMR spectra, FT-IR spectra, UV-Vis spectra, molar conductivity measurements, melting point measurements, magnetic susceptibility measurements, and LC-MS spectroscopic studies as well as by cyclic voltammetry.
Journal of Chemical Sciences, 2009
The novel vic-dioxime ligand containing the 4-amino-1-benzyl piperidine group, N,N′-(4amino-1-ben... more The novel vic-dioxime ligand containing the 4-amino-1-benzyl piperidine group, N,N′-(4amino-1-benzyl piperidine)-glyoxime, (LH 2 ) has been prepared from 4-amino-1-benzyl piperidine with anti-dichloroglyoxime at -15°C in absolute THF. Mononuclear Ni II metal complex has been obtained with 1 : 2 metal/ligand ratio. The Ni II complex of this ligand is proposed to be square planar geometry. IR spectra show that the ligand acts in a tetradentate manner and coordinates N 4 donor groups of LH 2 to Ni II ion. The detection of H-bonding (O-H⋅⋅⋅O) in the [Ni(LH) 2 ] (1) metal complex by IR spectra supported the square-planar MN 4 coordination of mononuclear complex. The disappereance of H-bonding (O-H⋅⋅⋅O) in the [Ni(L) 2 (BPh 2 ) 2 ] (2) complex shows that the BPh + 2 -capped groups (BPh + 2 cation formed BPh 4 anion) attaches to the main oxime core. MN 4 coordination of the [Ni(LH) 2 ] (1) and [Ni(L) 2 (BPh 2 ) 2 ] (2) metal complexes were also determined by 1 H-NMR spectroscopy. In the trinuclear Cu II -Ni II -Cu II metal complexes, the Ni II ion centered into the main oxime core by the coordination of the imino groups while the two Cu II ions coordinate dianionic oxygen donors of the oxime groups and linked to the ligands of 1,10-phenanthroline, 2,2′-bipyridine, and 4,4′-bipyridine. The ligand and their mono and trinuclear metal complexes were characterized by elemental analyses, FT-IR, UV-Vis, 1 H and 13 C-NMR spectra, magnetic susceptibility measurements, molar conductivity, cyclic voltammetry, mass spectra and X-ray powder techniques. The cyclic voltammetric results show that the cathodic peak potential of [Ni(L) 2 (BPh 2 ) 2 ] shifted toward more negative value compared to that of [Ni(LH) 2 ], probably due to a decreasing effect of back donation of metal-oxime moieties as a result of the BPh + 2 -bridged complex formation. Also, the formation of the trinuclear Cu II -Ni II -Cu II metal complexes caused considerable changes on the CV behaviour of mononuclear [Ni(LH) 2 ] (1) complex. The spectroelectrochemical study of [Ni(L) 2 (BPh 2 ) 2 ] (2) showed distinctive spectral changes that the intensity of the band (λ = at 364 nm, assigned to n → π* transitions) decreased and a new broad band in low intensity about 460 nm appeared as a result of the reduction of the nickel centered in the oxime core.
Transition Metal Chemistry, 2007
... Salih Ilhan and Hamdi Temel* Chemistry Department, Faculty of Education, Dicle University, Di... more ... Salih Ilhan and Hamdi Temel* Chemistry Department, Faculty of Education, Dicle University, Diyarbakir 21280 ... Ahmet Kilic Chemistry Department, Faculty of Arts and Sciences, Harran University, Sanliurfa 63100, Turkey ... reported for 2:1 and 1:1 electrolytes in these sol-vents. ...
Transition Metal Chemistry, 2008
Page 1. Novel vic-dioxime ligands and their poly-metal complexes bearing 1,8-diamino-3,6-dioxaoct... more Page 1. Novel vic-dioxime ligands and their poly-metal complexes bearing 1,8-diamino-3,6-dioxaoctane: synthesis, characterization, spectroscopy and electrochemistry Ahmet Kilic Æ Mustafa Durgun Æ Esref Tas Æ Ismail Yilmaz ...
Transition Metal Chemistry, 2006
... Ahmet Kilic and Esref Tas* Department of Chemistry, Harran University, 63510 Sanliurfa, Turke... more ... Ahmet Kilic and Esref Tas* Department of Chemistry, Harran University, 63510 Sanliurfa, TurkeyBahattin Gumgum Department of Chemistry, Dicle University, 21280 Diyarbakir, Turkey ... given in the Experimental section. Additional analyti-cal data are given in Tables 14. ...
Transition Metal Chemistry, 2000
A novel vic-dioxime, 1, 2 dihydroxyimino-1-p-tolyl-3-aza-6-morpholine heptane (LH 2) was prepared... more A novel vic-dioxime, 1, 2 dihydroxyimino-1-p-tolyl-3-aza-6-morpholine heptane (LH 2) was prepared by reacting anti-p-tolylchloroglyoxime with 4-(3-aminopropyl) morpholine in absolute THF. Mononuclear complexes with a metal–ligand ratio of 1: 2 were prepared ...
The Journal of Physical Chemistry B, 2001
The double-decker lutetium(III) phthalocyanine, Lu[(RS) 4 Pc] 2 , where R ) C 12 H 25 , was synth... more The double-decker lutetium(III) phthalocyanine, Lu[(RS) 4 Pc] 2 , where R ) C 12 H 25 , was synthesized and electrochemically characterized under several solution conditions. The neutral complex undergoes a single reversible one-electron oxidation and up to four reversible one-electron reductions in nonaqueous solutions of CH 2 Cl 2 or benzonitrile containing 0.1 M tetra-n-butylammonium perchlorate (TBAP), while one oxidation and five reductions are seen in aqueous 0.5 M KCl for a gel-like cast film membrane of Lu[(RS) 4 Pc] 2 in a tetraoctylphosphonium bromide (4C 8 P + Br -) matrix at a basal plane pyrolytic graphite electrode. The halfwave potentials for reduction of Lu[(RS) 4 Pc] 2 in CH 2 Cl 2 , 0.1 M TBAP are located at E 1/2 ) 0.04, -1.03, -1.36 and -1.73 V, while the single oxidation is located at E 1/2 ) 0.43 V vs SCE. These potentials, when measured vs Fc/Fc + , are negatively shifted by 0.20-0.46 V from the E 1/2 values obtained in the 0.5 M KCl solution where the electrogenerated anions of the double-decker complex are stabilized by the cations of the 4C 8 P + Brmatrix and five reductions are seen at E 1/2 ) 0.29, -0.66, -0.94, -1.22, and -1.41 V vs SCE. The fifth reduction has been theoretically predicted but had never before been observed for any doubledecker lutetium(III) phthalocyanine or related complex. A cast film of Lu[(RS) 4 Pc] 2 displays only one oxidation in the 0.5 M KCl solution (at E 1/2 ) 0.78 V vs SCE), and no reductions at all are seen in the absence of a matrix. An almost identical oxidation potential of E 1/2 ) 0.80 V is seen for oxidation of Lu[(RS) 4 Pc] 2 in KCl when dissolved in the cationic matrix. These half-wave potentials for oxidation in the cationic film, when measured vs Fc/Fc + , are thus more positive by more than 0.27-0.32 V than E 1/2 values measured in CH 2 Cl 2 or PhCN and this is consistent with a decreased degree of solvent or anion binding to {Lu[(RS) 4 Pc] 2 } + in the 4C 8 P + Brmatrix, as compared to what is observed in solution.
The Journal of Physical Chemistry B, 2003
The thermodynamics of ion paring between electrochemically reduced [(C 6 H 13 S) 8 Pc] 2 Lu or [(... more The thermodynamics of ion paring between electrochemically reduced [(C 6 H 13 S) 8 Pc] 2 Lu or [(C 12 H 25 S) 4 Pc] 2 Lu and a cationic tetra-n-octylphosphonium bromide (4C 8 P + Br -) matrix that was deposited in a gel-like cast film on a basal plane pyrolytic graphite electrode was investigated in an aqueous KCl solution that varied in concentration from 0.005 to 1.0 M. The purpose of this study was to elucidate ion-pairing effects between reduced double-decker lutetium(III) phthalocyanines with charges of -1 to -5 and cationic sites of the 4C 8 P + Brmatrix. Both phthalocyanines undergo five one-electron reductions in the film, and a linear relationship was observed between the measured half-wave potentials (E 1/2 ) for these processes and the Clconcentration of the electrolyte in the film. The apparent number of electrons transferred in each reduction step was obtained from plots of E 1/2 versus ln[Cl -], which gave Nernstian slopes of -23.5 ( 2.3 mV (or -54.1 ( 5.3 mV from plots of E 1/2 vs log[Cl -]) over a chloride concentration range of 0.005 to 1.0 M. The E 1/2 versus ln[Cl -] plots indicate that the stepwise addition of electrons to the phthalocyanines in the film is accompanied by a stepwise unit increase in the number of associated 4C 8 P + cations. Thus, the ratio of phthalocyanine molecules to monocations increases from 1:1 for the singly reduced derivative to 1:5 in the case of {[(C 6 H 13 S) 8 Pc] 2 Lu} 5or {[(C 12 H 25 S) 4 Pc] 2 Lu} 5-. This result leads to the conclusion that a binding of reduced [(C 6 H 13 S) 8 Pc] 2 Lu or [(C 12 H 25 S) 4 Pc] 2 Lu to the cationic sites of the 4C 8 P + matrix is responsible for the experimentally observed positive shift of the measured half-wave potentials as compared to E 1/2 values for the same electrode reactions in nonaqueous media. The changes in E 1/2 upon changing the electrolyte counter cation and/or the charge of the matrix are also described, and these results further support the observed ion-pairing effects that were examined by means of electrochemical and spectroscopic techniques.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2010
The synthesis, structure, spectroscopic and electro-spectrochemical properties of steric hindered... more The synthesis, structure, spectroscopic and electro-spectrochemical properties of steric hindered Schiff-base ligand [N,N -(3,4-benzophenon)-3,5-Bu t 2 -salicylaldimine (LH 2 )] and its mononuclear Cu(II), Co(II), Ni(II), Mn(II) and Fe(II) complexes are described in this work. The new dissymmetric steric hindered Schiff-base ligand containing a donor set of NONO was prepared through reaction of 3,4diaminobenzophenon with 3,5-Bu t 2 -salicylaldehyde. Certain metal complexes of this ligand were synthesized by treating an ethanolic solution of the ligand with an equimolar amount of metal salts. The ligand and its complexes were characterized by FT-IR, UV-vis, 1 H NMR, elemental analysis, molar conductivity and thermal analysis methods in addition to magnetic susceptibility, electrochemistry and spectroelectrochemistry techniques. The tetradentate and mononuclear metal complexes were obtained by reacting N,N -(3,4-benzophenon)-3,5-Bu t 2 -salicylaldimine (LH 2 ) with some metal acetate in a 1:1 mole ratio. The molar conductance data suggest metal complexes to be non-electrolytes.
Polyhedron, 2013
A new generation of soluble metallophthalocyanine derivatives (5a, 5b, 6a, 6b, 7b, 8b and 8b· 2KS... more A new generation of soluble metallophthalocyanine derivatives (5a, 5b, 6a, 6b, 7b, 8b and 8b· 2KSCN) bearing four 14-membered [1, 4, 8, 11] dioxadiaza macrocycles, 14-membered [1, 4, 8, 11] diazadithia-macrocycles or 14-membered [1, 4, 8, 11] diazadithia-macrocycles ...
Polyhedron, 2002
A new 18-membered ligand, 2,3-dibromo-6,7,13,14,15,16,22,23-octahydro 14, 15-bis(hydroxyimino)-tr... more A new 18-membered ligand, 2,3-dibromo-6,7,13,14,15,16,22,23-octahydro 14, 15-bis(hydroxyimino)-tribenzo [e,k,q] [1,4,10,13,7,16] diazadioxadithiacyclooctadecine (LH 4 ) containing three different heteroatoms (NÃ/, OÃ/, SÃ/) has been prepared from 1,2-bis (2?-amino phenylsulfanylethoxy)-4,5-dibromobenzene and cyanogen di-N -oxide. Mononuclear (LH 3 ) 2 M, where M0/ Ni(II), Cu(II), Co(II), Fe(II) binuclear (LH) 2 (UO 2 ) 2 (OH) 2 and trinuclear (LH) 2 M 3 , where M 0/Cu (II), Co (II) complexes of LH 4 have been obtained with a metal:ligand ratio 1:2, 2:2 and 3:2, respectively, through N ,N -coordinating or N, N, S, S-coordinating in the presence of a base, as do most of the vic -dioximes. 1 H NMR, IR, UV Á/Vis and MS data are presented. The cyclic voltammetric (CV) measurements of the newly synthesized compounds were measured. Voltammetric results showed that oxime-containing ligands stabilize Ni(III), Fe(III), Co(III) and Cu(III). The Fe(II) complex displayed a different behavior with respect to other complexes. This indicated that both Fe(III) and Fe(I) species are stable while oxime containing ligands tend to stabilize only one of the oxidized forms of the metal center of the complexes. Differently, ligand based reduction was recorded only with the Ni(II) complex. #
![Research paper thumbnail of The orthopalladation dinuclear [Pd(L1)(μ-OAc)]2, [Pd(L2)(μ-OAc)]2 and mononuclear [Pd(L3)2] complexes with [N, C, O] or [N, O] containing ligands: Synthesis, spectral characterization, electrochemistry and catalytic properties](https://attachments.academia-assets.com/40431904/thumbnails/1.jpg)
](Journal of Organometallic Chemistry, 2010
Treatment of the salicylaldimine ligands (L 1 H, L 2 H, L 3 H, L 4 H and L 5 H) with palladium(II... more Treatment of the salicylaldimine ligands (L 1 H, L 2 H, L 3 H, L 4 H and L 5 H) with palladium(II) acetate in absolute ethanol gave the orthopalladation dinuclear [Pd(L 1 )(l-OAc)] 2 , [Pd(L 2 )(l-OAc)] 2 and mononuclear [Pd(L 3 ) 2 ] with the tetradentate ligands [N, C, O] or [N, O] moiety. The ligands L 1 H and L 2 H are coordinated through the imine nitrogen and aromatic ortho carbon atoms, whereas the ligand L 3 H coordinated through the imine nitrogen and phenolic oxygens atoms. The Pd(II) complexes have a square-planar structure and were found to be effective catalysts for the hydrogenation of both nitrobenzene and cyclohexene. These metal complexes were also tested as catalysts in Suzuki-Miyaura coupling of aryl bromide in the presence of K 2 CO 3 . The catalytic studies showed that the introduction of different groups on the salicyl ring of the molecules effected the catalytic activity towards hydrogenation of nitrobenzene and cyclohexene in DMF at 25 and 45°C. The Pd(II) complexes easily prepared from cheap materials could be used as versatile and efficient catalysts for different C-C coupling reactions (Suzuki-Miyaura reactions). The structure of ligands and their complexes was characterized by UV-Vis, FT-IR, 1 H and 13 C NMR, elemental analysis, molar conductivity, as well as by electrochemical techniques.
... of topological analysis of electron density function derived from experimental X-ray ... MOME... more ... of topological analysis of electron density function derived from experimental X-ray ... MOMENTS OF A D0 METALLOCENE DERIVED BY ASSOCIATED PHOTOPHYSICAL AND DFT STUDY ... According to a method, based on solvatochromic shifts of absorption and emission ...
ChemInform, 2010
C, O] or [N, O] Containing Ligands: Synthesis, Spectral Characterization, Electrochemistry and Ca... more C, O] or [N, O] Containing Ligands: Synthesis, Spectral Characterization, Electrochemistry and Catalytic Properties. -(KILIC*, A.; KILINC, D.; TAS, E.; YILMAZ, I.; DURGUN, M.; OZDEMIR, I.; YASAR, S.; J. Organomet. Chem. 695 (2010) 5, 697-706; Dep. Chem., Univ. Harran, TR-63190 Sanliurfa, Turk.; Eng.) -Nuesgen 29-099
Transition Metal Chemistry, 2002
A novel (E,E)-dioxime and its mono-, di-and trinuclear complexes bearing tetradentate octyl sulfa... more A novel (E,E)-dioxime and its mono-, di-and trinuclear complexes bearing tetradentate octyl sulfanyl phenylamino substituents. Synthesis, characterization and electrochemical properties of its transition metal complexes Abstract A new vic-dioxime, 13,14-bis-(hydroxyimino)-9,12,15,18-diazadithiaoctacosane, has been synthesized from 2octylsulfanylaminobenzene and (E,E¢)-dichloroglyoxime. Mononuclear transition metal complexes of Ni II , Cu II , Co II and Fe II have been prepared and were found to have a metal-ligand ratio of 1:2. The synthesis of di-and trinuclear complexes was achieved with U IV O 2 and Cu II depending on the stoichiometry of the reactants. The complexes were characterized by elemental analysis, 1 H-n.m.r., u.v.-vis, i.r., f.a.b.-m.s. and by cyclic voltammetry.
Polyhedron, 2007
New Schiff-base copper and cobalt complexes,[Cu (L1)],[Cu (L2)] and [Co (L1)],[Co (L2)](where L1=... more New Schiff-base copper and cobalt complexes,[Cu (L1)],[Cu (L2)] and [Co (L1)],[Co (L2)](where L1= NN′-bis (3, 5-di-tert-butylsalicylaldimine)-1, 4-cyclohexane bis (methylamine) and L2= NN′-bis (3, 5-di-tert-butylsalicylaldimine)-1, 8-diamino-3, 6-...
Polyhedron, 2008
... Esref Tas a , Corresponding Author Contact Information , E-mail The Corresponding Author , Ah... more ... Esref Tas a , Corresponding Author Contact Information , E-mail The Corresponding Author , Ahmet Kilic a , Nazli Konak a and Ismail Yilmaz b , Corresponding Author Contact Information , E-mail The Corresponding Author. ...
Synthesis and Reactivity in Inorganic Metal-Organic and Nano-Metal Chemistry, 2009
... Esref Tas a , Hatice Kara b , Mustafa Durgun b , Ahmet Kilic b & Ismail Yilma... more ... Esref Tas a , Hatice Kara b , Mustafa Durgun b , Ahmet Kilic b & Ismail Yilmaz c pages 379-387. ... [ 25 26. Durmus, M., Ahsen, V., Luneau, D. and Pecaut. 2004. Synthesis and structures of morpholine substituted new vic-dioxime ligand and its Ni(II) complexes. J. Inorg. Chim. ...
Inorganica Chimica Acta, 2013
Journal of Coordination Chemistry, 2014
Journal of Organometallic Chemistry, 2014
ABSTRACT Herein we report the synthesis and characterization of a new series of synthesized mono-... more ABSTRACT Herein we report the synthesis and characterization of a new series of synthesized mono-and trinuclear cobaloxime/organocobaloximes from ketone that act as catalysts for cyclic carbonate synthesis from CO2 and epoxides under appropriate conditions (2 h, 100 degrees C and 1.6 MPa pressure). These reactions were carried out with and without co-catalyst, namely, 4-dimethylaminopyridine (DMAP), pyridine (py), triethyl amine (NEt3) or triphenyl phosphine (PPh3). In the catalytic experiments, the 4-dimethylaminopyridine (DMAP) was used as co-catalyst, since the DMAP was a more active base with higher yield compared to other Lewis bases. In addition, various factors influencing the cycloaddition reaction, such as co-catalyst, temperature, CO2 pressure and reaction time, were investigated. A dioxime ligand (LH2) (1) was obtained in two steps from 4-methylpropiophenone as ketone. Reaction of CoCl2.6H(2)O with the dioxime ligand (LH2) (1) and 4-tertbutyl pyridine afforded six-coordinate mononuclear cobaloxime or organocobaloxime (2-3) complexes. The mononuclear cobaloxime or organocobaloxime (2-3) complexes were used as precursors for building trinuclear cobaloximes or organocobaloxime (4-11) complexes. All compounds were fully characterized by H-1 and C-13 NMR spectra, FT-IR spectra, UV-Vis spectra, molar conductivity measurements, melting point measurements, magnetic susceptibility measurements, and LC-MS spectroscopic studies as well as by cyclic voltammetry.
Journal of Chemical Sciences, 2009
The novel vic-dioxime ligand containing the 4-amino-1-benzyl piperidine group, N,N′-(4amino-1-ben... more The novel vic-dioxime ligand containing the 4-amino-1-benzyl piperidine group, N,N′-(4amino-1-benzyl piperidine)-glyoxime, (LH 2 ) has been prepared from 4-amino-1-benzyl piperidine with anti-dichloroglyoxime at -15°C in absolute THF. Mononuclear Ni II metal complex has been obtained with 1 : 2 metal/ligand ratio. The Ni II complex of this ligand is proposed to be square planar geometry. IR spectra show that the ligand acts in a tetradentate manner and coordinates N 4 donor groups of LH 2 to Ni II ion. The detection of H-bonding (O-H⋅⋅⋅O) in the [Ni(LH) 2 ] (1) metal complex by IR spectra supported the square-planar MN 4 coordination of mononuclear complex. The disappereance of H-bonding (O-H⋅⋅⋅O) in the [Ni(L) 2 (BPh 2 ) 2 ] (2) complex shows that the BPh + 2 -capped groups (BPh + 2 cation formed BPh 4 anion) attaches to the main oxime core. MN 4 coordination of the [Ni(LH) 2 ] (1) and [Ni(L) 2 (BPh 2 ) 2 ] (2) metal complexes were also determined by 1 H-NMR spectroscopy. In the trinuclear Cu II -Ni II -Cu II metal complexes, the Ni II ion centered into the main oxime core by the coordination of the imino groups while the two Cu II ions coordinate dianionic oxygen donors of the oxime groups and linked to the ligands of 1,10-phenanthroline, 2,2′-bipyridine, and 4,4′-bipyridine. The ligand and their mono and trinuclear metal complexes were characterized by elemental analyses, FT-IR, UV-Vis, 1 H and 13 C-NMR spectra, magnetic susceptibility measurements, molar conductivity, cyclic voltammetry, mass spectra and X-ray powder techniques. The cyclic voltammetric results show that the cathodic peak potential of [Ni(L) 2 (BPh 2 ) 2 ] shifted toward more negative value compared to that of [Ni(LH) 2 ], probably due to a decreasing effect of back donation of metal-oxime moieties as a result of the BPh + 2 -bridged complex formation. Also, the formation of the trinuclear Cu II -Ni II -Cu II metal complexes caused considerable changes on the CV behaviour of mononuclear [Ni(LH) 2 ] (1) complex. The spectroelectrochemical study of [Ni(L) 2 (BPh 2 ) 2 ] (2) showed distinctive spectral changes that the intensity of the band (λ = at 364 nm, assigned to n → π* transitions) decreased and a new broad band in low intensity about 460 nm appeared as a result of the reduction of the nickel centered in the oxime core.
Transition Metal Chemistry, 2007
... Salih Ilhan and Hamdi Temel* Chemistry Department, Faculty of Education, Dicle University, Di... more ... Salih Ilhan and Hamdi Temel* Chemistry Department, Faculty of Education, Dicle University, Diyarbakir 21280 ... Ahmet Kilic Chemistry Department, Faculty of Arts and Sciences, Harran University, Sanliurfa 63100, Turkey ... reported for 2:1 and 1:1 electrolytes in these sol-vents. ...
Transition Metal Chemistry, 2008
Page 1. Novel vic-dioxime ligands and their poly-metal complexes bearing 1,8-diamino-3,6-dioxaoct... more Page 1. Novel vic-dioxime ligands and their poly-metal complexes bearing 1,8-diamino-3,6-dioxaoctane: synthesis, characterization, spectroscopy and electrochemistry Ahmet Kilic Æ Mustafa Durgun Æ Esref Tas Æ Ismail Yilmaz ...
Transition Metal Chemistry, 2006
... Ahmet Kilic and Esref Tas* Department of Chemistry, Harran University, 63510 Sanliurfa, Turke... more ... Ahmet Kilic and Esref Tas* Department of Chemistry, Harran University, 63510 Sanliurfa, TurkeyBahattin Gumgum Department of Chemistry, Dicle University, 21280 Diyarbakir, Turkey ... given in the Experimental section. Additional analyti-cal data are given in Tables 14. ...
Transition Metal Chemistry, 2000
A novel vic-dioxime, 1, 2 dihydroxyimino-1-p-tolyl-3-aza-6-morpholine heptane (LH 2) was prepared... more A novel vic-dioxime, 1, 2 dihydroxyimino-1-p-tolyl-3-aza-6-morpholine heptane (LH 2) was prepared by reacting anti-p-tolylchloroglyoxime with 4-(3-aminopropyl) morpholine in absolute THF. Mononuclear complexes with a metal–ligand ratio of 1: 2 were prepared ...
The Journal of Physical Chemistry B, 2001
The double-decker lutetium(III) phthalocyanine, Lu[(RS) 4 Pc] 2 , where R ) C 12 H 25 , was synth... more The double-decker lutetium(III) phthalocyanine, Lu[(RS) 4 Pc] 2 , where R ) C 12 H 25 , was synthesized and electrochemically characterized under several solution conditions. The neutral complex undergoes a single reversible one-electron oxidation and up to four reversible one-electron reductions in nonaqueous solutions of CH 2 Cl 2 or benzonitrile containing 0.1 M tetra-n-butylammonium perchlorate (TBAP), while one oxidation and five reductions are seen in aqueous 0.5 M KCl for a gel-like cast film membrane of Lu[(RS) 4 Pc] 2 in a tetraoctylphosphonium bromide (4C 8 P + Br -) matrix at a basal plane pyrolytic graphite electrode. The halfwave potentials for reduction of Lu[(RS) 4 Pc] 2 in CH 2 Cl 2 , 0.1 M TBAP are located at E 1/2 ) 0.04, -1.03, -1.36 and -1.73 V, while the single oxidation is located at E 1/2 ) 0.43 V vs SCE. These potentials, when measured vs Fc/Fc + , are negatively shifted by 0.20-0.46 V from the E 1/2 values obtained in the 0.5 M KCl solution where the electrogenerated anions of the double-decker complex are stabilized by the cations of the 4C 8 P + Brmatrix and five reductions are seen at E 1/2 ) 0.29, -0.66, -0.94, -1.22, and -1.41 V vs SCE. The fifth reduction has been theoretically predicted but had never before been observed for any doubledecker lutetium(III) phthalocyanine or related complex. A cast film of Lu[(RS) 4 Pc] 2 displays only one oxidation in the 0.5 M KCl solution (at E 1/2 ) 0.78 V vs SCE), and no reductions at all are seen in the absence of a matrix. An almost identical oxidation potential of E 1/2 ) 0.80 V is seen for oxidation of Lu[(RS) 4 Pc] 2 in KCl when dissolved in the cationic matrix. These half-wave potentials for oxidation in the cationic film, when measured vs Fc/Fc + , are thus more positive by more than 0.27-0.32 V than E 1/2 values measured in CH 2 Cl 2 or PhCN and this is consistent with a decreased degree of solvent or anion binding to {Lu[(RS) 4 Pc] 2 } + in the 4C 8 P + Brmatrix, as compared to what is observed in solution.
The Journal of Physical Chemistry B, 2003
The thermodynamics of ion paring between electrochemically reduced [(C 6 H 13 S) 8 Pc] 2 Lu or [(... more The thermodynamics of ion paring between electrochemically reduced [(C 6 H 13 S) 8 Pc] 2 Lu or [(C 12 H 25 S) 4 Pc] 2 Lu and a cationic tetra-n-octylphosphonium bromide (4C 8 P + Br -) matrix that was deposited in a gel-like cast film on a basal plane pyrolytic graphite electrode was investigated in an aqueous KCl solution that varied in concentration from 0.005 to 1.0 M. The purpose of this study was to elucidate ion-pairing effects between reduced double-decker lutetium(III) phthalocyanines with charges of -1 to -5 and cationic sites of the 4C 8 P + Brmatrix. Both phthalocyanines undergo five one-electron reductions in the film, and a linear relationship was observed between the measured half-wave potentials (E 1/2 ) for these processes and the Clconcentration of the electrolyte in the film. The apparent number of electrons transferred in each reduction step was obtained from plots of E 1/2 versus ln[Cl -], which gave Nernstian slopes of -23.5 ( 2.3 mV (or -54.1 ( 5.3 mV from plots of E 1/2 vs log[Cl -]) over a chloride concentration range of 0.005 to 1.0 M. The E 1/2 versus ln[Cl -] plots indicate that the stepwise addition of electrons to the phthalocyanines in the film is accompanied by a stepwise unit increase in the number of associated 4C 8 P + cations. Thus, the ratio of phthalocyanine molecules to monocations increases from 1:1 for the singly reduced derivative to 1:5 in the case of {[(C 6 H 13 S) 8 Pc] 2 Lu} 5or {[(C 12 H 25 S) 4 Pc] 2 Lu} 5-. This result leads to the conclusion that a binding of reduced [(C 6 H 13 S) 8 Pc] 2 Lu or [(C 12 H 25 S) 4 Pc] 2 Lu to the cationic sites of the 4C 8 P + matrix is responsible for the experimentally observed positive shift of the measured half-wave potentials as compared to E 1/2 values for the same electrode reactions in nonaqueous media. The changes in E 1/2 upon changing the electrolyte counter cation and/or the charge of the matrix are also described, and these results further support the observed ion-pairing effects that were examined by means of electrochemical and spectroscopic techniques.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2010
The synthesis, structure, spectroscopic and electro-spectrochemical properties of steric hindered... more The synthesis, structure, spectroscopic and electro-spectrochemical properties of steric hindered Schiff-base ligand [N,N -(3,4-benzophenon)-3,5-Bu t 2 -salicylaldimine (LH 2 )] and its mononuclear Cu(II), Co(II), Ni(II), Mn(II) and Fe(II) complexes are described in this work. The new dissymmetric steric hindered Schiff-base ligand containing a donor set of NONO was prepared through reaction of 3,4diaminobenzophenon with 3,5-Bu t 2 -salicylaldehyde. Certain metal complexes of this ligand were synthesized by treating an ethanolic solution of the ligand with an equimolar amount of metal salts. The ligand and its complexes were characterized by FT-IR, UV-vis, 1 H NMR, elemental analysis, molar conductivity and thermal analysis methods in addition to magnetic susceptibility, electrochemistry and spectroelectrochemistry techniques. The tetradentate and mononuclear metal complexes were obtained by reacting N,N -(3,4-benzophenon)-3,5-Bu t 2 -salicylaldimine (LH 2 ) with some metal acetate in a 1:1 mole ratio. The molar conductance data suggest metal complexes to be non-electrolytes.
Polyhedron, 2013
A new generation of soluble metallophthalocyanine derivatives (5a, 5b, 6a, 6b, 7b, 8b and 8b· 2KS... more A new generation of soluble metallophthalocyanine derivatives (5a, 5b, 6a, 6b, 7b, 8b and 8b· 2KSCN) bearing four 14-membered [1, 4, 8, 11] dioxadiaza macrocycles, 14-membered [1, 4, 8, 11] diazadithia-macrocycles or 14-membered [1, 4, 8, 11] diazadithia-macrocycles ...
Polyhedron, 2002
A new 18-membered ligand, 2,3-dibromo-6,7,13,14,15,16,22,23-octahydro 14, 15-bis(hydroxyimino)-tr... more A new 18-membered ligand, 2,3-dibromo-6,7,13,14,15,16,22,23-octahydro 14, 15-bis(hydroxyimino)-tribenzo [e,k,q] [1,4,10,13,7,16] diazadioxadithiacyclooctadecine (LH 4 ) containing three different heteroatoms (NÃ/, OÃ/, SÃ/) has been prepared from 1,2-bis (2?-amino phenylsulfanylethoxy)-4,5-dibromobenzene and cyanogen di-N -oxide. Mononuclear (LH 3 ) 2 M, where M0/ Ni(II), Cu(II), Co(II), Fe(II) binuclear (LH) 2 (UO 2 ) 2 (OH) 2 and trinuclear (LH) 2 M 3 , where M 0/Cu (II), Co (II) complexes of LH 4 have been obtained with a metal:ligand ratio 1:2, 2:2 and 3:2, respectively, through N ,N -coordinating or N, N, S, S-coordinating in the presence of a base, as do most of the vic -dioximes. 1 H NMR, IR, UV Á/Vis and MS data are presented. The cyclic voltammetric (CV) measurements of the newly synthesized compounds were measured. Voltammetric results showed that oxime-containing ligands stabilize Ni(III), Fe(III), Co(III) and Cu(III). The Fe(II) complex displayed a different behavior with respect to other complexes. This indicated that both Fe(III) and Fe(I) species are stable while oxime containing ligands tend to stabilize only one of the oxidized forms of the metal center of the complexes. Differently, ligand based reduction was recorded only with the Ni(II) complex. #
Journal of Organometallic Chemistry, 2010
Treatment of the salicylaldimine ligands (L 1 H, L 2 H, L 3 H, L 4 H and L 5 H) with palladium(II... more Treatment of the salicylaldimine ligands (L 1 H, L 2 H, L 3 H, L 4 H and L 5 H) with palladium(II) acetate in absolute ethanol gave the orthopalladation dinuclear [Pd(L 1 )(l-OAc)] 2 , [Pd(L 2 )(l-OAc)] 2 and mononuclear [Pd(L 3 ) 2 ] with the tetradentate ligands [N, C, O] or [N, O] moiety. The ligands L 1 H and L 2 H are coordinated through the imine nitrogen and aromatic ortho carbon atoms, whereas the ligand L 3 H coordinated through the imine nitrogen and phenolic oxygens atoms. The Pd(II) complexes have a square-planar structure and were found to be effective catalysts for the hydrogenation of both nitrobenzene and cyclohexene. These metal complexes were also tested as catalysts in Suzuki-Miyaura coupling of aryl bromide in the presence of K 2 CO 3 . The catalytic studies showed that the introduction of different groups on the salicyl ring of the molecules effected the catalytic activity towards hydrogenation of nitrobenzene and cyclohexene in DMF at 25 and 45°C. The Pd(II) complexes easily prepared from cheap materials could be used as versatile and efficient catalysts for different C-C coupling reactions (Suzuki-Miyaura reactions). The structure of ligands and their complexes was characterized by UV-Vis, FT-IR, 1 H and 13 C NMR, elemental analysis, molar conductivity, as well as by electrochemical techniques.