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Öğe 1,10-fenantrolinlerin indirgenmiş schiff bazları ve geçiş metal kompleksleri(2016) Aydemir, Murat; Baysal, Akın1.10-Fenantrolin şelat belirteçlerinin önemli bir sınıfını teşkil etmektedir. 1,10-Fenantrolin ve türevleri katalitik, redoks. fotoredoks özellikleri, biyolojik aktiviteleri ve supramoleküler kimyadaki kullanımları nedeni ile oldukça ilgi çekmektedirler. Hedeflenen ligandların sente/inde 2,9-dimetil-1.10-fenantrolin (neocuproine) başlangıç maddesi olarak kullanılmıştır. 2.9-Dimetil-1.10-fenantrolinin SeÛ2 ile yükseltgenmesi sonucu 1.10-fenantrolin-2,9-dikarbaldehit elde edilmiştir. 2,9-Bis(etanolamin)-l,10-fenantrolin ve 2,9- bis(etilendiamin)-l,10-fenantrolin ligandları. l,10-fenantrolin-2,9-dikarbaldehitin sırasıyla 1- aminoctanol ve etlendiamin ile tepkimesi ve bunu takiben NaBRı ile indirgenmesiyle hazırlanmıştır. Ligandlar hem yumuşak azot atomları ( fenantrolin halkasındaki ) hem de sert azot atomları ( sekonder amin grubundaki ) içermelerinden dolayı oldukça ilgi çekmektedir. 2.9-Bis(etanolamin)-l,10-fenantrolin ve 2,9-bis(etilendiamin)-l,10-fenantrolinin geçiş metalleri ( Co(II), Nİ(II). Cu(II). Zn(II), Pd(II), Pt(II) ) ile oluşturduğu koordinasyon kompleksleri hazırlanmış ve spektroskopik özellikleri incelenmiştir.Öğe Amine-functionalized graphene nanosheet-supported PdAuNi alloy nanoparticles: efficient nanocatalyst for formic acid dehydrogenation(Royal Soc Chemistry, 2018) Bulut, Ahmet; Yurderi, Mehmet; Kaya, Murat; Aydemir, Murat; Baysal, Akin; Durap, Feyyaz; Zahmakiran, MehmetFormic acid (HCOOH), a major by-product of biomass processing with high energy density, stability and non-toxicity, has a great potential as a safe and a convenient liquid hydrogen (H-2) storage material for combustion engines and fuel cell applications. However, high-purity hydrogen release from the catalytic decomposition of aqueous formic acid solution at desirable rates under mild conditions stands as a major challenge that needs to be solved for the practical use of formic acid in on-demand hydrogen generation systems. Described herein is a new nanocatalyst system comprised of 3-aminopropyltriethoxysilane-functionalized graphene nanosheet-supported PdAuNi alloy nanoparticles (PdAuNi/f-GNS), which can reproducibly be prepared by following double solvent method combined with liquid-phase chemical reduction, all at room temperature. PdAuNi/f-GNS selectively catalyzes the decomposition of aqueous formic acid through the dehydrogenation pathway (similar to 100% H-2 selectivity), in the absence of any promoting additives (alkali formates, Bronsted bases, Lewis bases, etc.). PdAuNi/f-GNS nanocatalyst provides CO-free H-2 generation with a turnover frequency of 1090 mol H-2 mol metal(-1) h(-1) in the additive-free dehydrogenation of formic acid at almost complete conversion (>= 92%) even at room temperature. The catalytic activity provided by PdAuNi/f-GNS nanocatalyst is higher than those obtained with the heterogeneous catalysts reported to date for the additive-free dehydrogenation of formic acid. Moreover, PdAuNi/f-GNS nanoparticles show high durability against sintering, clumping and leaching throughout the catalytic runs, so that the PdAuNi/f-GNS nanocatalyst retains almost its inherent catalytic activity and selectivity at the end of the 10th recycle.Öğe Aminophosphine ligands: synthesis, coordination chemistry, and activity of their palladium(II) complexes in Heck and Suzuki cross-coupling reactions(Springer, 2011) Kayan, Cezmi; Biricik, Nermin; Aydemir, MuratThe reaction of 4-aminodiphenylamine or 2-aminofluorene with two equivalents of PPh2Cl in the presence of Et3N gives new bis(diphenylphosphino) amines N,N-bis(diphenylphosphino)-4-aminodiphenylamine 1 and N, N-bis(diphenylphosphino)-2-aminofluorene 2 in good yields. Oxidation of 1 or 2 with hydrogen peroxide, elemental sulfur or gray selenium affords the corresponding chalcogen derivatives. The palladium and platinum complexes of these P-N-P donor ligands were prepared by the reaction of the bis(phosphino) amines with MCl2(cod) (M = Pd or Pt, cod = cycloocta-1,5-diene). All the new compounds have been characterized by analytical and spectroscopic methods, including H-1-P-31 NMR, H-1-C-13 HETCOR, or H-1-H-1 COSY correlation experiments. The Pd(II) complexes were investigated as catalysts in the Suzuki and Heck reactions; both showed good catalytic activity affording high yields of the desired products.Öğe Aminophosphine-palladium(II) complexes: Synthsesis, structure and applications in Suzuki and Heck cross-coupling reactions(Elsevier Science Sa, 2011) Aydemir, Murat; Baysal, Akin; Sahin, Ertan; Gumgum, Bahattin; Ozkar, SaimReaction of furfurylamine with 1 or 2 equivalents of PPh2Cl in the presence of Et3N, proceeds under anaerobic conditions in thf to give furfuryl-2-(N-diphenylphosphino)amine, Ph2PNHCH2-C4H3O, 1 and furfuryl-2-(N,N-bis(diphenylphosphino)amine), (Ph2P)(2)NCH2-C4H3O, 2, respectively. The reactions of 1 and 2 with MCl2(cod) (M = Pd, Pt; cod = 1,5-cyclooctadiene) or Pt(CH3)(2)(cod) yield complexes [M(Ph2PNHCH2-C4H3O)(2)Cl-2] (M= Pd 1a, Pt 1b), [Pt(Ph2PNHCH2-C4H3O)(2)(CH3)(2)] (1c), and [M((Ph2P)(2) NCH2-C4H3O)Cl-2] (M= Pd 2a, Pt 2b), [Pt((Ph2P)(2)NCH2-C4H3O)(CH3)(2)] (2c), respectively. All the compounds were isolated as analytically pure substances and characterized by NMR, IR spectroscopy and elemental analysis. Representative solid-state structures of 2a and 2b were also determined by X-ray single crystal diffraction technique. Furthermore, the palladium complexes 1a and 2a were tested and found to be highly active catalysts in the Suzuki coupling and Heck reaction affording biphenyls and trans-stilbenes, respectively. (C) 2011 Elsevier B.V. All rights reserved.Öğe Aniline based aminophosphine and cationic bis phosphino amine Ru II complexes: Investigation of catalytic activity in transfer hydrogenation of ketones(Dicle Üniversitesi, 2013) Kayan, Cezmi; Meriç, Nermin; Aydemir, Murat; Baysal, Akın; Temel, HamdiHydrogen transfer reduction processes are attracting increasing interest from synthetic chemists in viewof their operational simplicity. For this aim, a series of Ru II complexes with the NPP and NHP ligandswere synthesized starting from the complex [Ru ?6-p-simen µ-Cl Cl]2. The complexes were fullycharacterized by analytical and spectroscopic methods. Complexes 1-4 catalyze the transfer hydrogenationof a variety of simple alkyl and aryl alkyl ketones to secondary alcohols in the presence of iso-PrOH as thehydrogen source. Notably 3 acts as an excellent catalyst giving the corresponding alcohols in excellentconversions up to 99% TOF:198 h-1Öğe Application of half-sandwich metal-phosphinite compounds to biological activities: Determine the energies of the HOMO and LUMO levels(Wiley-V C H Verlag Gmbh, 2023) Meriç, Nermin; Rafikova, Khadichakhan; Zazybin, Alexey; Güzel, Remziye; Kayan, Cezmi; Karakas, Duygu Elma; Dündar, Abdurrahman; Aydemir, MuratMononuclear transition metal complexes 1-(furan-2-yl)ethyldiphenyl[dichloro(eta(6)-p-cymene)ruthenium(II)]phosphinite, (2), 1-(furan-2-yl)ethyldiphenyl[dichloro(eta(6)-benzene) ruthenium(II)] phosphinite (3), 1-(furan-2-yl)ethyldipheny[chloro(eta(4)-1,5-cyclooctadiene)rhodium(I)]phosphinite (4), 1-(furan-2-yl)ethyldiphenyl[dichloro (eta(5)pentamethylcyclopentadienyl)iridium (III)] phosphinite (5) were synthesized and characterized by microanalysis, infrared, MS, and NMR spectroscopy. The biological activities of the complexes were also tested. Compounds 2 and 5 were the best complexes at DPPH radical scavenging and reducing power activity at 73.27 % and 0.41 at 200 mu g/mL, respectively. The highest antimicrobial activity exhibited by complex 3 as 14 mm inhibition zone against S. aureus. All of the complexes have cleaved the DNA from the double-strand and exhibited three bands on gel electrophoresis. Moreover, cyclic voltammetry studies of the phosphinite complexes were carried out to determine the energies of the HOMO and LUMO levels as well as to estimate their electrochemical and some electronic properties.Öğe The application of novel boron complexes in asymmetric transfer hydrogenation of aromatic ketones(Pergamon-Elsevier Science Ltd, 2015) Temel, Hamdi; Pasa, Salih; Aydemir, MuratAsymmetric transfer hydrogenation using iso-PrOH as a hydrogen source offers an attractive route for reducing simple unsymmetrical functionalized ketones to chiral alcohols. The combined use of organometallic and coordination chemistry has produced a number of new and powerful synthetic methods for important classes of compounds in general and for optically active substances in particular. For this aim, the (S,Z)-1-((1-hydroxy butane-2-yl imino)methyl)naphthalene-2-ol chiral ligand was chosen to obtain boron complexes. Boronic derivative compounds such as phenylboronic acid, 6-methoxynaphthalen-2-ylboronic acid, 4-methyl-3-nitrophenylboronic acid and 1,4-phenylenediboronic acid were applied to obtain complexation with chiral based ligands. The structures of these ligands and their complexes have been elucidated by a combination of multinuclear NMR spectroscopy, LC MS/MS, TGA/DTA, UV Vis., elemental analysis, XRD, SEM, and FTIR. These boron complexes have also been tested as catalysts in the enantioselective transfer hydrogenation of acetophenone derivatives to afford the corresponding product, (S)-1-phenylethanol with high conversions (up to 99%) and modest enantioselectivities (up to 70% ee). The substituents on the backbone of the ligands had a significant effect on both the activity and % ee. (C) 2015 Elsevier Ltd. All rights reserved.Öğe Application of phthalocyanine complexes of Cu(II), Co(II), Ni(II), and Zn(II) as catalysts in the transfer hydrogenation of acetophenone and its derivatives(Elsevier Ltd., 2024) Namlı, Mesut; Işık, Uğur; Kantar, Cihan; Aydemir, MuratIn this study, tetra substituted metallophthalocyanines (M: Ni, Zn, Co, and Cu) containing imine and azo groups were synthesized using microwave irradiation. The structures of all complexes have been totally characterized via 1HNMR, 13CNMR, TGA/DTA, LC-MS/MS, elemental analysis, UV–Vis, FT-IR spectroscopy. The comparison of the catalytic features of phthalocyanine based on metals is also discussed briefly. These phthalocyanine-complexes were also used in the transfer hydrogenation (TH) of acetophenone derivatives in the existence of KOH, utilizing isoPrOH as a hydrogen source. Acetophenone compounds determined a TH of up to 99 % conversion. Copper phthalocyanines were first used as catalysts in transfer hydrogenation reactions. The Cu(II) complexes showed higher catalytic activity, converting up to 97 % at 1.0 mol% catalyst loading. Furthermore, we have discovered that the catalytic characteristics of this class of molecules are significantly influenced by both steric and electronic variables.Öğe The application of tunable tridendate P-based ligands for the Ru(II)-catalysed transfer hydrogenation of various ketones(Wiley, 2014) Meriç, Nermin; Durap, Feyyaz; Aydemir, Murat; Baysal, Akın; 0000-0001-7294-6792; 0000-0003-0899-1948Two novel versatile tridendate aminophosphine-phosphinite and phosphinite ligands were prepared and their trinuclear neutral ruthenium(II) dichloro complexes were found to be effective catalysts for the transfer hydrogenation of various ketones in excellent conversions up to 99% in the presence of 2-propanol/NaOH in 0.1M isopropanol solution. Particularly, [Ru-3(PPh2OC2H4)(2)N-PPh2((6)-p-cymene)(3)Cl-6] acts as an excellent catalyst giving the corresponding alcohols in excellent conversion up to 99% (turnover frequency1176h(-1)). A comparison of the catalytic properties of the complexes is also discussed briefly. Furthermore, the structures of these ligands and their corresponding complexes have also been clarified using a combination of multinuclear NMR spectroscopy, infrared spectroscopy and elemental analysis. H-1-C-13 HETCOR or H-1-H-1 COSY correlation experiments were used to confirm the spectral assignments. Copyright (c) 2014 John Wiley & Sons, Ltd.Öğe Applications of transition metal complexes containing 3,3?-bis(diphenylphosphinoamine)-2,2?-bipyridine ligand to transfer hydrogenation of ketones(Elsevier Science Sa, 2012) Aydemir, Murat; Meric, Nermin; Baysal, AkinHydrogen transfer reduction processes are attracting increasing interest from synthetic chemists in view of their operational simplicity. 3,3'-bis(diphenylphosphinoamine)-2,2'-bipyridine, (Ph2PNH)(2)C10H6N2, was prepared through a single step reaction of 3,3'-diamino-2,2'-bipyridine with diphenyl-chlorophosphine. Reaction of (Ph2PNH)(2)C10H6N2 with [Ru(eta(6)-benzene)(mu-Cl)Cl](2), [Rh(mu-Cl)(cod)](2) or [Ir(eta(5)-C5Me5)(mu-Cl)Cl](2) gave a range of new bridged dinuclear complexes (C10H6N2{NHPPh2Ru(eta(6)-benzene)Cl-2}(2)], 1, [C10H6N2{PPh2NHRh(cod)Cl}(2)], 2 and [C10H6N2{NHPPh2Ir(eta(5)-C5Me5)Cl-2}(2)], 3, respectively. All new complexes have been fully characterized by analytical and spectroscopic methods. (HP)-H-1-P-31{H-1} NMR, (HC)-H-1-C-13 HETCOR or (HH)-H-1-H-1 COSY correlation experiments were used to confirm the spectral assignments. 1, 2 and 3 are suitable catalyst precursors for the transfer hydrogenation of acetophenone derivatives. Notably [Ru((Ph2PNH)(2)C10H6N2)(eta(6)-benzene)Cl-2], 1 acts as an excellent catalyst, giving the corresponding alcohols in 98-99% yields in 10 min at 82 degrees C (TOF <= 600 h(-1)) for the transfer hydrogenation reaction in comparison to analogous rhodium or iridium complexes. This transfer hydrogenation is characterized by low reversibility under these conditions. (C) 2012 Elsevier B.V. All rights reserved.Öğe Applications of transition metal complexes containing aminophosphine ligand to transfer hydrogenation of ketones(Wiley, 2011) Aydemir, Murat; Baysal, Akın; Turgut, Yılmaz; 0000-0001-7294-6792Hydrogen transfer reduction processes are attracting increasing interest from synthetic chemists in view of their operational simplicity. Reaction of [Ph2PNHCH2-C4H3S] with [Ru(eta(6)-benzene)(mu-Cl)Cl](2), [Rh(mu-Cl)(cod)](2) and [Ir(eta(5)-C5Me5)(mu-Cl)Cl](2) gave a range of new monodendate complexes [Ru(Ph2PNHCH2-C4H3S)(eta(6)-benzene)Cl-2], 1, [Rh(Ph2PNHCH2-C4H3S)(cod)Cl], 2, and [Ir(Ph2PNHCH2-C4H3S)(eta(5)-C5Me5)Cl-2], 3, respectively. All new complexes were fully characterized by analytical and spectroscopic methods. H-1-P-31 NMR, H-1-C-13 HETCOR or H-1-H-1 COSY correlation experiments were used to confirm the spectral assignments. 1-3 are suitable catalyst precursors for the transfer hydrogenation of acetophenone derivatives. Notably [Ru(Ph2PNHCH2-C4H3S)(eta(6)-benzene) Cl-2], 1, acts as an excellent catalyst, giving the corresponding alcohols in 98-99% yields in 30 min at 82 degrees C (TOF <= 200 h(-1)) for the transfer hydrogenation reaction in comparison to analogous rhodium or iridium complexes. This transfer hydrogenation is characterized by low reversibility under these conditions. Copyright (C) 2011 John Wiley & Sons, Ltd.Öğe Asymmetric transfer hydrogenation of acetophenone derivatives with novel chiral phosphinite based ?6-p-cymene/ruthenium(II) catalysts(Elsevier Science Sa, 2011) Aydemir, Murat; Meric, Nermin; Baysal, Akin; Turgut, Yilmaz; Kayan, Cezmi; Seker, Sevil; Togrul, MahmutEnantioselective reduction of prochiral ketones to optically active secondary alcohols is an important subject in synthetic organic chemistry because the resulting chiral alcohols are extremely useful, biologically active compounds. The new chiral ligands (2R)-2-[benzyl{(2-((diphenylphosphanyl)oxy)ethyl)}amino]butyldiphenylphosphinite, 1 and (2R)-2-[benzyl{(2-((dicyclohexylphosphanyl)oxy)ethyl)}amino]butyldicyclohexylphosphinite, 2 and the corresponding ruthenium(II) complexes 3 and 4 have been prepared. The structures of these complexes have been elucidated by a combination of multinuclear NMR spectroscopy, IR spectroscopy and elemental analysis. P-31-{H-1} NMR, DEPT, H-1-C-13 HETCOR or H-1-H-1 COSY correlation experiments were used to confirm the spectral assignments. These ruthenium(II) ephosphinite complexes have been used as catalysts for the asymmetric transfer hydrogenation of acetophenone derivatives. Under optimized conditions, aromatic ketones were reduced in good conversions and in moderate to good enantioselectivities (up to 85% ee). (C) 2011 Elsevier B. V. All rights reserved.Öğe Asymmetric transfer hydrogenation of alkyl/aryl or alkyl/methyl ketones catalyzed by known C2-symmetric ferrocenyl-based chiral bis(phosphinite)-Ru(II), Rh(I) and Ir(III) complexes(Elsevier Science Sa, 2016) Durap, Feyyaz; Karakas, Duygu Elma; Ak, Bunyamin; Baysal, Akin; Aydemir, MuratKnown Ru(II), Rh(I) and Ir(III) complexes of C-2-symmetric ferrocenyl based chiral bis(phoshinite) ligands were catalyzed the asymmetric transfer hydrogenation of alkyl/aryl or alkyl methyl ketones. Corresponding secondary alcohols were obtained with high enantioselectivities up to 98% ee and reactivities using iso-propanol as the hydrogen source. (C) 2016 Elsevier B.V. All rights reserved.Öğe Asymmetric transfer hydrogenation of aromatic ketones with the ruthenium(II) catalyst derived from C2 symmetric N,N?-bis[(1S)-1-benzyl-2-O-(diphenylphosphinite)ethyl]ethanediamide(Elsevier Science Sa, 2010) Aydemir, Murat; Meric, Nermin; Durap, Feyyaz; Baysal, Akin; Togrul, MahmutAsymmetric transfer hydrogenation of ketones with chiral molecular catalysts is realized to be one of the most magnificent tools to access chiral alcohols in organic synthesis. A new chiral phosphinite compound N,N'-bis[(1S)-1-benzyl-2-O-(diphenylphosphinite)ethyl]ethanediamide (1), has been synthesized by the reaction of chlorodiphenylphosphine with N,N'-bis[(1S)-1-benzyl-2-hydroxyethyl]ethanediamide under argon atmosphere. The oxidation of 1 with aqueous hydrogen peroxide, elemental sulfur or grey selenium in toluene gave the corresponding oxide 1a, sulfide 1b and selenide 1c, respectively. Pd, Pt and Ru complexes were obtained by the reaction of 1 with [MCl2(cod)] (M: Pd 1d, Pt 1e) and [Ru(p-cymene)Cl-2](2) 1f, respectively. All these new complexes were characterized by using NMR, FT-IR spectroscopies and microanalysis. Additionally, as a demonstration of their catalytic reactivity, the ruthenium complex 1f was tested as catalyst in the asymmetric transfer hydrogenation reactions of acetophenone derivatives with iPrOH was also investigated. (C) 2010 Elsevier B.V. All rights reserved.Öğe Bimetallic PdxNi1-x and PdxCo1-x nanoparticles supported on K-OMS-2: Highly active, environmentally friendly and reusable nanocatalysts for the Suzuki–Miyaura cross-coupling reactions in water(Wiley, 2021) Durap, Feyyaz; Gülen, Yasemin; Abay, Ayşe; Bulut, Ahmet; Yurderi, Mehmet; Aydemir, Murat; Baysal, Akın; 0000-0003-0899-1948; 0000-0002-5520-0558; 0000-0001-5472-4213; 0000-0002-1697-8623; 0000-0002-0233-8940; 0000-0002-4238-5012; 0000-0001-7294-6792; 0000-0002-5633-3811Addressed herein is the catalysis of bimetallic PdxNi1-x and PdxCo1-x nanoparticles (NPs) supported on a cryptomelane-type manganese oxide (K-OMS-2) solid for the Suzuki-Miyaura cross-couplings of phenylboronic acid with various aryl halides. Bimetallic PdxNi1-x and PdxCo1-x NPs were prepared by using a conventional one-step impregnation-reduction method. Among these catalysts with different compositions of Ni and Pd or Co and Pd, the Pd0.2Ni0.8 and Pd0.2Co0.8 catalysts showed the highest activity in the Suzuki-Miyaura cross-couplings of various aryl halides including iodides, bromides, and even chlorides with phenylboronic acid in ambient air and water under reflux conditions. The Suzuki-Miyaura cross-coupling reaction proceeded efficiently in the presence of Pd0.2Ni0.8@K-OMS-2 and Pd0.2Co0.8@K-OMS-2 NPs under the optimized conditions in water. Pd0.2Ni0.8@K-OMS-2 and Pd0.2Co0.8@K-OMS-2 NPs provided high conversions up to 98% and 99% and turnover frequencies of 11,760 and 11,880 h(-1) in the cross-coupling of phenylboronic acid with 1-bromo-4-nitrobenzene. More importantly, these new supported Pd0.2Ni0.8@K-OMS-2 and Pd0.2Co0.8@K-OMS-2 NPs were found to be highly durable nanocatalyst throughout the reusability experiments, and they maintain almost their inherent activity after 10th and 5th catalytic cycle, respectively. Bimetallic Pd0.2Ni0.8@K-OMS-2 and Pd0.2Co0.8@K-OMS-2 NPs were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy with energy dispersive X-ray (SEM-EDX), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ICAPQ inductively coupled plasma mass spectroscopy (ICP-MS) analyses.Öğe Biological assays and theoretical density functional theory calculations of Rh(I), Ir(III), and Ru(II) complexes of chiral phosphinite ligand(Wiley, 2020) Rafikova, Khadichakhan; Binbay, Nil Ertekin; Meriç, Nermin; Kerimkulova, Aygül; Zazybin, Alexey; Binbay, Veysel; Okumuş, Veysi; Kayan, Cezmi; Işık, Uğur; Aydemir, Murat; 0000-0003-1010-9563; 0000-0002-2488-0378; 0000-0001-8028-2244; 0000-0002-6244-9327Four metal complexes, IL-OPPh2-Ru-p-cymene (3), IL-OPPh2-Ru-benzene (4), IL-OPPh2-Ir-Cp* (5), IL-OPPh2-Rh-COD (6), have been evaluated for in vitro antioxidant activity such as 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging and reducing power activity. Maximum scavenging activity (71.43%) was obtained with IL-OPPh2-Ru-p-cymene, whereas IL-OPPh2-Rh-COD showed the highest reducing power ability. The complexes were also studied for their antimicrobial activity against three Gram-positive and three Gram-negative bacteria. In addition, DNA binding of the complexes was evaluated using calf thymus DNA. Both Ru(II) complexes exhibited good DNA-binding activity while the other complexes did not have any activity. Furthermore, ab initio quantum calculations of four complexes were also carried out using density functional theory to better understand their chemical behaviors.Öğe Biological assays, electrochemical behavior, and theoretical DFT calculations of Ru(II) complexes of chiral phosphinite based based on ?-amino alcohols: Transfer hyrogenation of ketones using a HCOOH/Et3N mixture(Elsevier B.V., 2024) Khadichakhan, Rafikova; Meriç, Nermin; Binbay, Nil Ertekin; Okumuş, Veysi; Sever, M. Şerif; Belyankova, Yelizaveta; Aydemir, MuratSynthesis of two phosphinite ligands based on β-amino alcohols, in high yields has been demonstrated. When we treated [Ru(arene)(μ-Cl)Cl]2 {arene:p-cymene,benzene} with chelating phosphinite ligands, we obtained neutral Ru(II)-complexes possessing the general formula [Ru(arene)phosphiniteCl2]. The structure of the ligands and complexes was confirmed using analytical and spectroscopic techniques. The quantum chemical calculations were carried out for the ruthenium complexes at the DFT/CAM-B3LYP level of theory in gas phase. The phosphinite complexes were subjected to cyclic voltammetry studies in order to determine the energies of HOMO and LUMO levels and to estimate their electrochemical and some electronic properties. Organic complex-based memory substrates were immobilized using TiO2-modified ITO electrodes, and the memory functions of phosphinite-based organic complexes were verified by chronoamperometry (CA) and open-circuit potential amperometry (OCPA). In the present study, the antioxidant potentials of ruthenium-based p-cymene and benzene complexes through DPPH radical scavenging, metal chelating, and reducing power activities were also determined. In addition, DNA binding abilities and antimicrobial activities of these complexes against pathogenic bacteria were studied. Finally, the ruthenium complex, (2S)-1-{[(2S)-2-[(diphenylphosphanyl)oxy]propyl][(1R)-1-phenylethyl]amino}propan-2-yldiphenyl phosphinitobis[dichloro(η6-benzene)ruthenium(II)] also catalyzed asymmetric transfer hydrogenation of acetophenone with high conversion (up to 99%) and good enantioselectivity (ee up to 89 %), in the existence of formic acid and triethylamine in dichloromethane medium under air atmosphere.Öğe Bis(phosphinite) with C2-Symmetric Axis; Effects on the Ruthenium(II)-Catalyzed Asymmetric Transfer Hydrogenation of Acetophenone Derivatives(Georg Thieme Verlag Kg, 2012) Aydemir, Murat; Durap, Feyyaz; Kayan, Cezmi; Baysal, Akin; Turgut, YilmazChiral ruthenium catalyst systems generated in situ from [Ru(eta(6)-p-cymene)(mu-Cl)Cl](2) complex and chiral C-2-symmetric bis(phosphinite) ligands based on amino alcohol derivatives were employed in the asymmetric transfer hydrogenation of aromatic ketones to give the corresponding optically active alcohols in high yield. The best results were obtained in the [Ru(eta(6)-p-cymene)(mu-Cl)Cl](2) and (2S)-2-[benzyl(2-{benzyl[(2S)-1-[(diphenylphosphanyl)oxy]-3-phenyl propan-2-yl]amino}ethyl)amino]-3-phenylpropyl diphenylphosphinite or (2R)-2-[benzyl(2-{benzyl[(2R)-1-[(diphenylphosphanyl) oxy]-3-phenylpropan-2-yl]amino}ethyl) amino]-3-phenylpropyl diphenylphosphinite catalytic systems, which gave enantioselectivities of up to 93% ee and 99% conversion.Öğe Boron containing chiral Schiff bases: Synthesis and catalytic activity in asymmetric transfer hydrogenation (ATH) of ketones(Elsevier, 2020) Pasa, Salih; Arslan, Nevin; Meric, Nermin; Kayan, Cezmi; Bingul, Murat; Durap, Feyyaz; Aydemir, MuratAsymmetric Transfer Hydrogenation (ATH) has been an attractive way for the reduction of ketones to chiral alcohols. A great number of novel and valuable synthetic pathways have been achived by the combination usage of organometallic and coordination chemistry for the production of important class of compounds and particularly optically active molecules. For this aim, four boron containing Schiff bases were synthesized by the reaction of 4-formylphenylboronic acid with chiral amines. The boron containing structures have been found as stable compounds due to the presence of covalent B-O bonds and thus could be handled in laboratory environment. They were characterized by H-1 NMR and FT-IR spectroscopy and elemental analysis and they were used as catalyst in the transfer hydrogenation of ketones to the related alcohol derivatives with high conversions (up to 99%) and low enantioselectivities (up to 22% ee). (C) 2019 Elsevier B.V. All rights reserved.Öğe Catalysts for the asymmetric transfer hydrogenation of various ketones from [3-[(2S)-2-[(diphenylphosphanyl)oxy]-3-phenoxypropyl]-1-methyl-1H-imidazol-3-ium chloride] and [Ru(?6-arene)(?-Cl)Cl]2, Ir(?5-C5Me5)(?-Cl)Cl]2 or [Rh(?-Cl)(cod)]2(Elsevier Science Sa, 2019) Meric, Nermin; Arslan, Nevin; Kayan, Cezmi; Rafikov, Khadichakhan; Zazybin, Alexey; Kerimkulova, Aygul; Aydemir, MuratThe combination of [3-[(2S)-2-[(diphenylphosphanyl)oxy]-3-phenoxypropyl]-1-methyl-1H-imidazol-3-ium chloride] with [Ru(eta(6)-arene)(mu-Cl)Cl](2), Ir(eta(5)-C5Me5)(mu-Cl)Cl](2) or [Rh(mu-Cl)(cod)](2), in the presence of KOH/isoPrOH, has been found to generate catalysts that are capable of enantioselectively reducing alkyl, aryl ketones to the corresponding (R)-alcohols. Under optimized conditions, when the catalysts were applied to the asymmetric transfer hydrogenation, we obtained the secondary alcohol products in high conversions and enantioselectivities using only 0.5 mol% catalyst loading. In addition, [3-[(2S)-2-{[(chloro(eta(4)-1,5-cyclooctadiene)rhodium)diphenyl phosphanyl] oxy}-3-phenoxypropyl]-1-methyl-1H-imidazol-3-ium chloride], (6) complex is much more active than the other analogous complexes in the transfer hydrogenation. Catalyst 6 acts as excellent catalysts, giving the corresponding (R)-1-phenyl ethanol in 99% conversion in 30 min (TOF <= 396 h(-1)) and in high enantioselectivity (92% ee).