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Öğe 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, AlexeyThe 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.Öğe Kiral Fosfinit Ligandları Içeren Yeni Rutenyum(II) Komplekslerinin Sentezi ve Ketonların Asimetrik Transfer Hidrojenasyon Reaksiyonundaki Katalitik Aktivitelerinin Arastırılması(2015) Kayan, Cezmi; Gürbüz, Nevin; Karakaplan, Mehmet; Aydemir, MuratEtkin kiral fosfor ligandların özellikle kiral iskelet yapısına sahip olanların geliştirilmesine yönelik çalışmalar asimetrik katalizin en öncelikli konuları arasında yeralmaktadır. Gu?nu?mu?ze kadar, fosfin ve metal-fosfin komplekslerinin sentezine yönelik çok çaba harcanmış olmasına rağmen, benzer yapıdaki bis(fosfinitler) yeterince araştırılmamıştır. Fosfin ligandları metal katalizli asimetrik dönu?şu?mlerde oldukça yaygın uygulama alanları bulmuştur. Ancak, fosfinitler fosfinlerle kıyaslandığında farklı kimyasal, elektronik ve yapısal özelliklere sahip olmaları bu ligandları daha da ilgi çekici kılmaktadır. Örneğin, fosfinitlerdeki metal fosfor bağı fosfinlerdeki bağ ile kıyaslandığında, elektron çekici P-OR grubundan dolayı daha gu?çlu?du?r. Ayrıca, fosfinitlerdeki P(OR)R2 boş ?* orbitalinin varlığı, fosfiniti daha iyi bir alıcı konumuna getirerek kararlı duruma getirebilmektedir. Ancak, fosfinitlerin analogları olan fosfinlere göre en bu?yu?k avantajı hazırlanmalarındaki kolaylıktır. İlgili ketonların indirgenmesi sonucu elde edilen kiral sekonder alkoller, ticari açıdan önemli birçok farmasötikler, zirai maddeler, parfu?mler, tatlandırıcılar ve özel materyaller için anahtar konumundaki madde görevi u?stlenir. Asimetrik sentez genellikle çok bu?yu?k miktarlarda nispeten du?şu?k maliyetli kiral u?ru?nler sağlama avantajı nedeniyle en çok dikkat çeken yöntem olarak kabul edilir. Ketonların ilgili kiral alkollere asimetrik dönu?şu?mu? için kullanılan en bilinen yöntemler hidrosililasyon, hidroborasyon, biyoindirgeme ve katalitik (transfer) hidrojenasyon olarak sayılabilir. Bu yöntemde karbonil bileşiklerini ilgili alkollere dönu?ştu?rmek için hidrojen kaynağı olarak sekonder alkoller (2- propanol v.b.) kullanılır. Böylece, moleku?ler hidrojen kullanılması nedeniyle ortaya çıkabilecek patlama riski ortadan kaldırılır. Üstelik bu reaksiyonda kullanılan 2-propanol’ u?n oldukça kararlı, çalışılması kolay, anti-toksik ve ucuz olması da metodun diğer avantajlarındandır. Bu projede; ilk olarak birbirinden farklı kiral bileşiklerden yola çıkılarak regioseçici epoksit halka açılması yöntemiyle kiral amino alkoller hazırlanmıştır. Sonraki basamakta ise kiral aminoalkoller PPh2Cl etkileştirilerek kiral fosfinit tu?revleri sentezlenmiştir. Hazırlanan yeni kiral fosfinit bileşikleri Ru[(?6-p-simen)Cl2]2 ve Ru[(?6-benzen)Cl2]2 ile etkileştirilerek yeni Ru(II) geçiş metal kompleksleri sentezlenmiş ve bu komplekslerin yapıları NMR, IR, LC- ESI-IT-TOF MS ve element analizi ile aydınlatılmıştır. Son olarak elde edilen komplekslerin, ketonların asimetrik transfer hidrojenasyon reaksiyonlarında kiral katalizör olarak kullanımları araştırılmıştır.Öğe 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, MuratA 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.Öğe New functional chiral P-based ligands and application in ruthenium-catalyzed enantioselective transfer hydrogenation of ketones(Pergamon-Elsevier Science Ltd, 2017) Meric, Nermin; Kayan, Cezmi; Gurbuz, Nevin; Karakaplan, Mehmet; Binbay, Nil Ertekin; Aydemir, MuratMetal-catalyzed asymmetric transfer hydrogenation is a powerful and practical method for the reduction of ketones to produce the corresponding secondary alcohols, which are valuable building blocks in the pharmaceutical, perfume, and agrochemical industries. Hence, a series of novel chiral beta-amino alcohols were synthesized by chiral amines with regioselective ring opening of (S)-propylene oxide or reaction with (S)-(+)-2-hydroxypropyl p-toluenesulfonate by a straightforward method. The chiral ruthenium catalytic systems generated from [Ru(arene)(mu-Cl)Cl](2) complexes and chiral phosphinite ligands based on amino alcohol derivatives were employed in asymmetric transfer hydrogenation of ketones to give the corresponding optically active alcohols; (2S)-1-([(2.9-2-[(diphenylphosphanypoxylpropyl][(1R)-1-phenylethyl]amino}propan-2-yldiphenylphosphinitobis[dichol-oro(eta(6)-benzene)ruthenium(II)] acts an excellent catalyst in the reduction of cl-naphthyl methyl ketone, giving the corresponding alcohol with up to 99% ee. The substituents on the backbone of the ligands were found to have a remarkable effect on both the conversion and enantioselectivity of the catalysts. Furthermore, this transfer hydrogenation is characterized by low reversibility under these conditions. (C) 2017 Elsevier Ltd. All rights reserved.Öğe 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, ErtanThe 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.Öğe Synthesis and characterization of new (N-diphenylphosphino)-isopropylanilines and their complexes: crystal structure of (Ph2P=S)NH-C6H4-4-CH(CH3)2 and catalytic activity of palladium(II) complexes in the Heck and Suzuki cross-coupling reactions(Wiley, 2010) Aydemir, Murat; Baysal, Akin; Gurbuz, Nevin; Ozdemir, Ismail; Gumgum, Bahattin; Ozkar, Saim; Caylak, NagihanThree new (N-diphenylphosphino)-isopropylanilines, having isopropyl substituent at the carbon 2- (1) 4- (2) or 2,6- (3) were prepared from the aminolysis of chlorodiphenylphosphine with 2-isopropylaniline,4-isopropylaniline or 2,6-diisopropylaniline, respectively, under anaerobic conditions. Oxidation of 1,2 and 3 with aqueous hydrogen peroxide, elemental sulfur or gray selenium gave the corresponding oxides, sulfides and selenides (Ph2P=E)NH-C6H4-2-CH(CH3)(2), (Ph2P=E)NH-C6H4-4-CH(CH3)(2) and (Ph2P=E)NH-C6H4-2,6-[CH(CH3)(2)](2), where E = O, S, or Se, respectively. The reaction of [M(cod)Cl-2] (M = Pd, Pt; cod = 1,5-cyclooctadiene) with two equivalents of 1,2 or 3 yields the corresponding monodendate complexes [M((Ph2P)NH-C6H4-2-CH(CH3)(2))(2)Cl-2], M = Pd 1d, M = Pt 1e, [M((Ph2P)NH-C6H4-4-CH(CH3)(2))(2)Cl-2], M = Pd 2d, M = Pt 2e and [M((Ph2P)NH-C6H4-2,6-(CH(CH3)(2))(2))(2)Cl-2], M = Pd 3d, M = Pt 3e, respectively. All the compounds were isolated as analytically pure substances and characterized by NMR, IR spectroscopy and elemental analysis. Furthermore, representative solid-state structure of [(Ph2P=S)NH-C6H4-4-CH(CH3)(2)] (2b) was determined using single crystal X-ray diffraction technique. The complexes 1d-3d were tested and found to be highly active catalysts in the Suzuki coupling and Heck reaction, affording biphenyls and stilbenes, respectively. Copyright (C) 2009 John Wiley & Sons, Ltd.Öğe 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, AlexeyThe 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.
