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    Ionic liquid based Ru(II)-phosphinite compounds and their catalytic use in transfer hydrogenation: X-ray structure of an ionic compound 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol
    (Pergamon-Elsevier Science Ltd, 2014) Aydemir, Murat; Rafikova, Khadichakhan; Kystaubayeva, Nurzhamal; Pasa, Salih; Meric, Nermin; Ocak, Yusuf Selim; Zazybin, Alexey
    The compound 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol chloride (1) was prepared from the reaction of 1-methylimidazole with epichlorohydrine. The corresponding phosphinite ligands were synthesized by the reaction 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol chloride, [C7H15N2OCl]Cl with one equivalent of chlorodiphenylphosphine or chlorodicyclohexylphosphine, in anhydrous CH2Cl2 and under an inert argon atmosphere. [Ru(eta(6)-arene)(mu-Cl)Cl](2) dimers readily react with the phosphinite ligands [(Ph2PO)-C7H14N2Cl]Cl (2) or [(Cy2PO)-C7H14N2Cl]Cl (3) at room temperature to afford the cationic derivatives [Ru((Ph2PO)-C7H14N2Cl)(eta(6)-arene)Cl-2]Cl and [Ru((Cy2PO)-C7H14N2Cl)(eta(6)-arene)Cl-2]Cl {arene: benzene (4), (5); p-cymene (6), (7)}. The structures of these ligands and their corresponding complexes have been elucidated by a combination of multinuclear NMR and IR spectroscopy, TGA/DTA and elemental analysis. The molecular structure of the ionic compound 1 was also determined by an X-ray single crystal diffraction study. Furthermore, the catalytic activity of complexes 4-7 for the transfer hydrogenation of various ketones was investigated and these complexes were found to be efficient catalysts in the transfer hydrogenation of various ketones, with excellent conversions up to 99%. Specifically, [Ru((Cy2PO)-C7H14N2Cl)(eta(6)-benzene)Cl-2]Cl (5) and [Ru((Cy2PO)-C7H14N2Cl)(eta(6)-p-cymene)Cl-2]Cl (7) act as excellent catalysts, giving the corresponding alcohols in 98-99% conversions in 5 min (TOF <= 1188 h(-1)). (C) 2014 Elsevier Ltd. All rights reserved.
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    A new class of well-defined ruthenium catalysts for enantioselective transfer hydrogenation of various ketones
    (Elsevier Science Sa, 2018) Kayan, Cezmi; Meric, Nermin; Rafikova, Khadichakhan; Zazybin, Alexey; Gurbuz, Nevin; Karakaplan, Mehmet; Aydemir, Murat
    A pair of novel optically pure phosphinite ligands were synthesized by ring opening reaction of chiral amines with (R)-styrene oxide or (S)-glycidyl phenyl ether oxide using a straightforward method in high yields and their ruthenium complexes were described in detail. The ruthenium complexes proved to be highly efficient catalysts for the enantioselective hydrogenation of ketones, affording products up to 99% ee. The results showed that the corresponding chiral alcohols could be obtained with high activity and excellent enantioselectivities at the desired temperature. (2S)-1-{benzyl[(1S)-1-(naphthalen-1-yl)ethyl]amino}-3-phenoxypropan-2-yl diphenylphosphinito[dichloro(eta(6)-benzene)ruthenium (II)] acts an excellent catalyst in the reduction of ketones, giving the corresponding alcohol up to 99% ee. (C) 2018 Elsevier B.V. All rights reserved.
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    Transfer hydrogenation of ketones catalyzed by new rhodium and iridium complexes of aminophosphine containing cyclohexyl moiety and photosensing behaviors of rhodium and iridium based devices
    (Elsevier Science Sa, 2014) Rafikova, Khadichakhan; Kystaubayeva, Nurzhamal; Aydemir, Murat; Kayan, Cezmi; Ocak, Yusuf Selim; Temel, Hamdi; Zazybin, Alexey
    The reaction of [Rh(mu-Cl)(cod)](2) and Ir(eta(5)-C5Me5)(mu-Cl)Cl](2) with aminophosphine ligands Cy2PNHCH2-C4H3X (X: O; S) gave a range of new monodendate [Rh(Cy(2)PNHCH(2)eC(4)H(3)O)(cod) Cl], (1), [Rh(Cy(2)PNHCH(2)eC(4)H3S)(cod) Cl], (2), [Ir(Cy2PNHCH2-C4H3O)(h(5)-C5Me5)Cl-2], (3) and [Ir(Cy2PNHCH2 -C4H3S)(eta(5)-C5Me5)Cl-2], (4) complexes, which were characterized by analytical and spectroscopic methods. The new rhodium(I) and iridium(III) catalysts were applied to transfer hydrogenation of acetophenone derivatives using 2-propanol as a hydrogen source. The results showed that the corresponding alcohols could be obtained with high activity (up to 99%) under mild conditions. Notably, [Rh(Cy2PNHCH2-C4H3O)(cod)Cl] complex (1) is much more active than the other analogous complexes in the transfer hydrogenation. Moreover, organiceinorganic rectifying contacts were fabricated forming rhodium(I) and iridium(III) complex thin films on n-Si semiconductors and evaporating Au metal on the structures. Electrical properties of the contacts including ideality factor, barrier height and series resistance were determined using their currentevoltage (IeV) data. The photoelectrical characteristics of the devices were examined under the light with 40-100 mW/cm(2) illumination conditions. It was seen that light had strong effects on IeV characteristics of the devices and the ones fabricated using 3 and 4 complexes had unusually forward and reverse bias photoconducting behavior. (C) 2014 Elsevier B.V. All rights reserved.