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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 Aminofosfin (AMP) türü ligandların sentezi, karakterizasyonu ve bazı geçiş metal komplekslerinin hazırlanması(2017) Durap, Feyyaz; Gümgüm, BahattinFosfor ile azot arasında doğrudan bağ bulunan bileşikler son birkaç on yıldan beri bilinmektedir. P-N bağları içeren bileşikler kimyasına katkıda bulunmak üzere bu çalışmada; anilin türevleri (2,3-dimetilanilin, 2,4-dimetilanilin, 2,5-dimetilanilin, 2,6-dimetilanilin, 2- etilanilin ve 4-etilanilin) ile monoklorodifenilfosfinin (Ph2PCl) reaksiyonundan PIII tipi P-N-P iskeletine sahip altı yeni multidentat ligand, bis(difenilfosfino)anilin [R-N(PPh2)2] sentezlenmiştir. Sentezlenen bu ligandların PV tipi kalkojenleri (O, S, Se) ve Pt(II) ve Cu(I) kompleks bileşikleri hazırlanmıştır. Ayrıca etilendiamin türevi, P(O)Ph2NHCH2CH2NHP(O)Ph2, (P(O)Ph2)2NCH2CH2NHP(O)Ph2, (PPh2)2NCH2CH2N(PPh2)2, (P(E)Ph2)2NCH2CH2N(P(E)Ph2)2 (E: O, S, Se) gibi PV ve PIII tipi yeni aminofosfin bileşikleri ile (PPh2)2NCH2CH2N(PPh2)2 ligandının Pt(II) kompleks bileşiği sentezlenmiştir. Elde edilen tüm ligand ve komplekslerin karakterizasyonu NMR, IR, element analizi ve tek kristali elde edilen bileşikler için X-ışınları spektroskopisiyle yapılmıştır. Anahtar Kelimeler: Aminofosfin (AMP), difosfinoamin, kalkojen, organofosfor bileşikleri, P-N bağları.Öğe Application of N,N-bis(diphenylphosphino) aniline palladium(II) complexes as pre-catalysts in Heck coupling reactions(Wiley, 2007) Gümgüm, Bahattin; Biricik, Nermin; Durap, Feyyaz; Özdemir, İsmail; Guerbuez, Nevin; Ang, Wee Han; Dyson, Paul J.; 0000-0003-0899-1948Palladium(II) complexes with N,N-bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre-catalysts have been determined by single-crystal X-ray diffraction. Copyright (c) 2007 John Wiley & Sons, Ltd.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 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 Benzylation of benzene and toluene with benzylchloride over clay-based acid catalysts(Mrs Pushpa Agarwal, 2006) Durap, Feyyaz; Akcay, Mehmet; Yurdakoc, KadirThe pillared clay catalysts were calcined after in corporation of metal polycation ions with exchangeable cations and water. Friedel-Crafts alkylations of aromatic hydrocarbons were carried out in the presence of clay catalysts originating from bentonite. In these reactions, it has been found that pillared clays have excellent catalytic activity. It was found that iron pillared clay (Fe-PILC) was the more efficient catalyst producing quantitative conversion with greatly reduced amounts of catalysts in short reaction period. Their efficiency is attributed to the higher Fe3+, Cr3+ and Al3+ contents in the catalysts and pillaring effect. The clays have both Bronsted and Lewis acidities which were determined by pyridine adsorption-desorption and in situ FTIR technique.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 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 Catechol-type ligand containing new modular design dioxaborinane compounds: Use in the transfer hydrogenation of various ketones(Elsevier Science Bv, 2018) Kilic, Ahmet; Kaya, Ibrahim Halil; Ozaslan, Ismail; Aydemir, Murat; Durap, FeyyazA novel class of tricoordinate dioxaborinane compounds, which have the general formula [B-1(L1-5)] and [B-2(L1-5)], were designed and synthesized by the corresponding catechol-type ligands (L-1-L-5) at ambient temperature. All the new compounds were fully characterized by NMR (H-1, C-13, and B-11), FT-IR, UV-vis, LC-MS spectroscopy, and melting point analysis and microanalysis. The dioxaborinane [B-1(L1-5)] and [B-2(L1-5)] compounds were investigated as catalyst for the transfer hydrogenation of various ketones under suitable conditions. Particularly, it was proved that the ferrocene-based dioxaborinane [B-1(L1-5)] molecules can afford an efficient catalytic conversion compared to corresponding 3,5-bis(trifluoromethyl)phenyl-based [B-2(L1-5)] dioxaborinanes in transfer hydrogenation catalytic studies.Öğe The chiral boronate-catalyzed asymmetric transfer hydrogenation of various aromatic ketones to high-value alcohols: Preparation and spectroscopic studies(Elsevier Science Sa, 2019) Kilic, Ahmet; Durgun, Mustafa; Durap, Feyyaz; Aydemir, MuratThis work deals with the synthesis, spectroscopic studies and catalytic evaluation of the novel chiral salen (L1H2) and (L2H2) ligands and their chiral boronate [L-1(B1-4)] and [L-2(B1-4)] complexes. Initially, the reaction of 5-azidomethyl salicylaldehyde and (R)-(-)-2-amino-1-butanol in absolute ethanol afforded a new chiral salen ligand (L1H2). Then, a novel chiral salen ligand (L2H2) have been prepared from chiral salen ligand (L1H2) for the synthesis of boronate [L-2(B1-4)] complexes through click reaction approach under ambient conditions. The reaction of chiral salen (L1H2) and (L2H2) ligands with various boronic acids afforded a new tetra-coordinated mononuclear chiral boronate [L-1(B1-4)] and [L-2(B1-4)] complexes. All the compounds are remarkably stable crystalline solids and were obtained in good yields. For the full characterization of newly synthesized chiral salen ligands and their boronate complexes, the FT-IR, UV-Vis, NMR (H-1, C-13, and B-11), LC-MS, and elemental analysis techniques have been used. The well-shaped chiral boronate compounds were investigated as catalyst for the asymmetric transfer hydrogenation (ATH) of aromatic ketones under appropriate settings. Particularly, it was proved that the ferrocene-based boronate compounds can afford an efficient catalytic conversion compared to the other boronate complexes in the asymmetric transfer hydrogenation catalytic studies. (C) 2019 Elsevier B.V. All rights reserved.Öğe Chiral C2-symmetric ?6-p-cymene-Ru(II)-phosphinite complexes: Synthesis and catalytic activity in asymmetric reduction of aromatic, methyl alkyl and alkyl/aryl ketones(Elsevier Science Sa, 2018) Karakas, Duygu Elma; Aydemir, Murat; Durap, Feyyaz; Baysal, AkinChiral C-2-symmetric bis(phosphinite) ligands and their binuclear ruthenium(II) complexes have been synthesized and used as catalysts in the ruthenium-catalyzed asymmetric transfer hydrogenation of aromatic, methyl alkyl and alkyl/aryl ketones using 2-propanol as both the hydrogen source and solvent in the presence of KOH. Under optimized conditions, all complexes showed high catalytic activity as catalysts in the reduction of various ketones to corresponding chiral secondary alcohols. Products were obtained with high conversions (99%) and moderate to good enantioselectivities (82% ee). Furthermore, C2-symmetric bis(phosphinite) ligands and their binuclear ruthenium(II) complexes were characterized by multinuclear NMR spectroscopy, FT-IR spectroscopy, LC/MS-MS and elemental analysis. (C) 2017 Elsevier B.V. All rights reserved.Öğe Chiral phosphinites as efficient ligands for enantioselective Ru(II), Rh(I) and Ir(III)-catalyzed transfer hydrogenation reactions(Springer, 2017) Baysal, Akin; Karakas, Duygu Elma; Meric, Nermin; Ak, Bunyamin; Aydemir, Murat; Durap, FeyyazMetal-catalyzed enantioselective transfer reduction of ketones to enantiomerically enriched chiral alcohols has recently attracted attention. Therefore, a series of methyl alkyl or alkyl/aryl ketones have been reduced by using Ru(II), Rh(I) and Ir(III) catalysts based on C (2)-symmetric chiral ferrocenyl phosphinite ligands. The corresponding optically active secondary alcohols were obtained in excellent conversions and moderate-to-good enantioselectivities. The best results were obtained with an iridium catalyst, giving up to 98% conversion and 80% ee.Öğe Cross-coupling reactions in water using ionic liquid-based palladium(II)-phosphinite complexes as outstanding catalysts(Wiley, 2014) Meriç, Nermin; Aydemir, Murat; Işık, Uğur; Ocak, Yusuf Selim; Rafikova, Khadichakhan; Paşa, Salih; Kayan, Cezmi; Durap, Feyyaz; Temel, Hamdi; Zazybin, Alexey G.; 0000-0003-0899-1948; 0000-0002-6244-9327; 0000-0002-4792-8821Two new phosphinite ligands based on ionic liquids [(Ph2PO)C7H14N2Cl]Cl (1) and [(Cy2PO)C7H14N2Cl]Cl (2) were synthesized by reaction of 1-(3-chloro-2-hydoxypropyl)-3-methylimidazolium chloride, [C7H15N2OCl]Cl, with one equivalent of chlorodiphenylphosphine or chlorodicyclohexylphosphine, respectively, in anhydrous CH2Cl2 and under argon atmosphere. The reactions of 1 and 2 with MCl2(cod) (M=Pd, Pt; cod=1,5-cyclooctadiene) yield complexes cis-[M([(Ph2PO)C7H14N2Cl]Cl)(2)Cl-2] and cis-[M(Cy2PO)C7H14N2Cl]Cl)(2)Cl-2], respectively. All complexes were isolated as analytically pure substances and characterized using multi-nuclear NMR and infrared spectroscopies and elemental analysis. The catalytic activity of palladium complexes based on ionic liquid phosphinite ligands 1 and 2 was investigated in Suzuki cross-coupling. They show outstanding catalytic activity in coupling of a series of aryl bromides or aryl iodides with phenylboronic acid under the optimized reaction conditions in water. The complexes provide turnover frequencies of 57 600 and 232 800h(-1) in Suzuki coupling reactions of phenylboronic acid with p-bromoacetophenone or p-iodoacetophenone, respectively, which are the highest values ever reported among similar complexes for Suzuki coupling reactions in water as sole solvent in homogeneous catalysis. Furthermore, the palladium complexes were also found to be highly active catalysts in the Heck reaction affording trans-stilbenes. Copyright (c) 2014 John Wiley & Sons, Ltd.Öğe Dihydrogen Phosphate Stabilized Ruthenium(0) Nanoparticles: Efficient Nanocatalyst for The Hydrolysis of Ammonia-Borane at Room Temperature(Mdpi Ag, 2015) Durap, Feyyaz; Caliskan, Salim; Ozkar, Saim; Karakas, Kadir; Zahmakiran, MehmetIntensive efforts have been devoted to the development of new materials for safe and efficient hydrogen storage. Among them, ammonia-borane appears to be a promising candidate due to its high gravimetric hydrogen storage capacity. Ammonia-borane can release hydrogen on hydrolysis in aqueous solution under mild conditions in the presence of a suitable catalyst. Herein, we report the synthesis of ruthenium(0) nanoparticles stabilized by dihydrogenphosphate anions with an average particle size of 2.9 +/- 0.9 nm acting as a water-dispersible nanocatalyst in the hydrolysis of ammonia-borane. They provide an initial turnover frequency (TOF) value of 80 min(-1) in hydrogen generation from the hydrolysis of ammonia-borane at room temperature. Moreover, the high stability of these ruthenium(0) nanoparticles makes them long-lived and reusable nanocatalysts for the hydrolysis of ammonia-borane. They provide 56,800 total turnovers and retain similar to 80% of their initial activity even at the fifth catalytic run in the hydrolysis of ammonia-borane at room temperature.Öğe Effect of initial configuration on DFT calculations for transition metal complexes(Osman SAĞDIÇ, 2019) Binbay, Nil E.; Binbay, Veysel; Aydemir, Murat; Durap, Feyyaz; Meriç, Nermin; Kayan, Cezmi; Arslan, NevinComputational methods, which solves the Schrödinger’s equation for molecules, have become an indispensable tool in last decades.And Density Functional Theory is one of the most used, and most effective computational method.Transition Metal complexes, on the other hand, have been being used extensively in many important applications in many fields, suchas chemical catalysts, atomic thin films, and pharmaceutical industry. Applying computational methods to transition metal complexeshas become inevitable to understand better, to control and to design these compounds.As it is known, it is very difficult to handle transition metals computationally, mostly due to near degeneracy in their electronic states.The computational algorithms usually cannot achieve as successive result as they can do for other typical elements, like carbon ornitrogen for instance. Computational methods are needed to be improved for properly deal with transition metal complexes. To findcomputationally cheaper but still effective methods to deal with these complexes is a major challenge.Unlike the analogue calculations, computational methods solve all equations iteratively, so there are major differences between thesetwo calculation types. The starting point in state space (the assumed initial conformation of molecule) is could have a stronger effectthen the expected, on the flow of the iterative solving algorithm of the computational approach.Here we present a comparative study for a Ruthenium complex. We have optimised the molecule several times. Each of the optimisationsstarted from different initial molecular conformations. Then we have compared the result in different ways, like calculation times andminimum energy that had reached, to see effect of starting configurations on the calculation.It is showed that, starting configuration is an important parameter for computational calculations of transition metal complexes, and itis needed to be carefully chosen to improve success of calculations.Öğe Ferrocene based chiral binuclear η6-benzene-Ru(II)-phosphinite complexes: Synthesis, characterization and catalytic activity in asymmetric reduction of ketones(Wiley, 2018) Al-bayati, Yaser W. Abdlhmed; Karakaş, Duygu Elma; Meriç, Nermin; Aydemir, Murat; Durap, Feyyaz; Baysal, Akın; 0000-0001-7294-6792; 0000-0003-0899-1948; 0000-0003-2582-9993In the present study, a series of chiral C-2-symmetric ferrocenyl based binuclear (6)-benzene-Ru(II) complexes bearing diphenylphosphinite and diisopropylphosphinite moieties have been synthesised. The new binuclear (6)-benzene-Ru(II)-phosphinite complexes were characterised based on nuclear magnetic resonance (H-1, C-13, P-31-NMR), FT-IR spectroscopy and elemental analysis. Then, these complexes have been screened as catalytic precursors in the transfer hydrogenation of acetophenone with 2-propanol as both the hydrogen source and solvent in the presence of KOH. The corresponding optically active secondary alcohols were obtained in excellent conversion rates between 96 and 99% and moderate to good enantioselectivities (up to 78% ee). The complex 5 was the most efficient catalyst among the four new complexes investigated herein.Öğe The first application of C2-symmetric ferrocenyl phosphinite ligands for rhodium-catalyzed asymmetric transfer hydrogenation of various ketones(Elsevier Science Sa, 2015) Ak, Bunyamin; Aydemir, Murat; Durap, Feyyaz; Meric, Nermin; Baysal, AkinHomogeneous catalysis has been responsible for many major recent developments in synthetic organic chemistry. 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, a new class of chiral modular C-2-symmetric ferrocenyl phosphinite ligands has been prepared in good yields by using the inexpensive 1,1'-ferrocenedicarboxyaldehyde and various ferrocene based-amino alcohols as starting materials, and applied in the rhodium(I)-catalyzed asymmetric transfer hydrogenation (ATH) of aromatic ketones to give corresponding secondary alcohols with excellent enantioselectivities and reactivities using isoPrOH as the hydrogen source (up to 99% conversion and 99% ee). The substituents on the backbone of the ligands are found to exhibit a remarkable effect on both the activity and % ee. The structures of these ligands and their complexes have been elucidated by a combination of multinuclear NMR spectroscopy, IR spectroscopy and elemental analysis. (C) 2015 Elsevier B.V. All rights reserved.Öğe Half-sandwich ruthenium(II) and iridium(III) complexes of imidazole based phosphinite ligands: antioxidant and antibacterial activities as well as electrochemical properties(John Wiley and Sons Inc, 2024) Işık, Uğur; Rafikova, Khadichakhan; Meriç, Nermin; Güzel, Remziye; Kerimkulova, Aygül; Akimbek, Arailym; Okumuş, Veysi; Durap, Feyyaz; Kayan, Cezmi; Aydemir, MuratRuthenium(II) and iridium(III) complexes of phosphinites including imidazole moiety were synthesized and characterized by microanalysis, IR, MS, and NMR spectroscopies. Antibacterial activity against Gram-positive and Gram-negative bacterial strains was assessed in all complexes. The highest radical scavenging (72.2 %) was obtained for [3-(3-chloro-2-({[dichloro(η6-benzene)ruthenium]diphenylphosphanyl}oxy)propyl)-1-butyl-1H-imidazol-3-ium chloride], 4 at 200 μg/mL concentration, while [3-(3-chloro-2-({[dichloro(η5-pentamethylcyclopentadienyl)-iridium]diphenylphosphanyl}oxy)pro-pyl)-1-butyl-1H-imidazol-3-ium chloride], 6 demonstrated the highest antibacterial activity as 13 mm inhibition zone against E. hirea. Furthermore, optical and electrochemical featured of metal complexes containing imidazole phosphinite were investigated utilizing UV–vis absorption and cyclic voltammetry techniques. Consequently, all complexes can be proposed as metal-based charge convertible phosphinite complexes which may be employed as new generation and synergistic Dye-Sensitized Solar Cell (DSSC) materials.
