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    Ruthenium, rhodium and iridium complexes of the furfuryl-2-(N-diphenylphosphino)methylamine ligand: Molecular structure and catalytic activity
    (Pergamon-Elsevier Science Ltd, 2012) Kayan, Cezmi; Meric, Nermin; Aydemir, Murat; Baysal, Akin; Elma, Duygu; Ak, Bunyamin; Sahin, Ertan
    The reaction of furfurylamine with two equivalents of PPh2Cl in the presence of Et3N affords furfuryl-2-(N,N-bis(diphenylphosphino)amine), (Ph2P)(2)NCH2-C4H3O (1). The corresponding ruthenium(II) complex trans-[Ru((PPh2)(2)NCH2-C4H3O)(2)Cl-2] (3) was synthesized by reacting 1 with [Ru(eta(6)-p-cymene)(mu-Cl)Cl](2). The reaction of furfurylamine with one equivalent of PPh2Cl gives Ph2PNHCH2-C4H3O (2). The reaction of 2 with [Ru(eta(6)-p-cymene)(mu-Cl)Cl](2), [Ru(eta(6)-benzene)(mu-Cl)Cl](2), [Rh(mu-Cl)(cod)](2) and [Ir(eta(5)-C5Me5)(mu-Cl)Cl](2) yields the complexes [Ru(Ph2PNHCH2-C4H3S)(eta(6)-p-cymene)Cl-2] (4), [Ru(Ph2PNHCH2-C4H3O)(eta(6-)benzene)Cl-2] (5), [Rh(Pb2PNHCH2-C4H3O)(cod)Cl] (6) and [Ir(Ph2PNHCH2-C4H3O)(eta(5)-C5Me5)Cl-2] (7), respectively. All the complexes were isolated from the reaction solution and fully characterized by analytical and spectroscopic methods. The structure of [Ru(Ph2PNHCH2-C4H3O)(eta(6)-p-cymene)Cl-2] (4) was also determined by single crystal X-ray diffraction. Complexes 3-7 are suitable precursors forming highly active catalysts in the transfer hydrogenation of a variety of simple ketones. Notably, the catalysts obtained by using the ruthenium complexes [Ru(Ph2PNHCH2-C4H3O)(eta(6)-p-cymene)Cl-2] (4) and [Ru(Ph2PNHCH2-C4H3O)(eta(6)-benzene)Cl-2] (5) are much more active in the transfer hydrogenation, converting the carbonyls to the corresponding alcohols in 97-99% yields (TOF <= 300 h(-1)), compared to analogous rhodium and iridium complexes and the trans-Ru(II)-p-cymene bis(phosphino)amine complex. (c) 2012 Elsevier Ltd. All rights reserved.
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    Synthesis, characterization, and application to transfer hydrogenation of ?6-(3,4,5-trimethoxybenzyl)-?1-N-heterocyclic carbene-ruthenium complex
    (Taylor & Francis Ltd, 2011) Demir, Serpil; Ozdemir, Ismail; Cetinkaya, Bekir; Sahin, Ertan; Arici, Cengiz
    A new chelating ruthenium complex was synthesized using an electron-rich olefin and [RuCl2(p-cymene)](2) and characterized structurally and spectroscopically. The structure of the complex was verified using X-ray crystallography. The complex displayed high activities in transfer hydrogenation.
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    Synthesis, crystal structures, magnetic properties and Suzuki and Heck coupling catalytic activities of new coordination polymers containing tetracyanopalladate(II) anions
    (Pergamon-Elsevier Science Ltd, 2013) Senocak, Aysegul; Karadag, Ahmet; Yerli, Yusuf; Gurbuz, Nevin; Ozdemir, Ismail; Sahin, Ertan
    Four novel coordination polymers, [Ni(bishydeten)Pd(CN)(4)] (1), [Cu(bishydeten)Pd(CN)(4)] (2), [Zn(bishydeten)Pd(CN)(4)] (3) and [Cd(bishydeten)Pd(CN)(4)] (4) (bishydeten = N,N'-bis(2-hydroxyethyl)ethylenediamine], have been synthesized and characterized by various techniques (elemental analysis, IR, EPR, X-ray and thermal analysis). In compound 4, all of the cyano groups use -N edges to form coordination bonds to Cd(II) in addition to -C atoms, resulting in the formation of a tridimensional network. The same situation is observed for compound 3 for one of the tetracyanopalladate(II) groups, while two cyano groups remain in the monodentate form coordinated to Pd(II) in the other tetracyanopalladate(II) group. While an EPR signal was not observed for 1, the g parameters obtained from the EPR spectrum of 2 indicated that the Cu(II) ions are located in tetragonal distorted octahedral sites (D-4h) and that the ground state of the paramagnetic electron is d(x2-y2). Variable temperature magnetic susceptibility measurements recorded in the range 15-300 K showed the presence of a very small antiferromagnetic interaction below 20 K for complexes 1 and 2.2 was proven to be less effective as a catalyst than 1 under the Heck reaction conditions. Moreover, 1 was determined to be a more effective catalyst and more efficient for iodoarenes than bromoarenes under Suzuki coupling conditions. (c) 2012 Elsevier Ltd. All rights reserved.