
handle: 11454/4321
This thesis is concerned with pirazol substituted arene ruthenium compounds. Arene metal complexes have been extensively investigated by organic and organometallic chemists for over 50 years. Arene ruthenium complexes play an increasingly important role in organometallic chemistry. Within the large family of ? 6-arene ruthenium complexes, piano-stool complexes are undeniably the most studied ones. They have found applications in catalysis supramolecular assemblies, molecular devices, and have shown antiviral, antibiotic, and anticancer activities They appear to be good starting materials for access to reactive arene metal hydrides intermediates that have been used recently for carbon-hydrogen bond activation.This thesis consists of three parts. The first part is a concise review on synthesis of arene ruthenium complexes their derivatives. In part II the experimental details were given. In part III, results of arene ruthenium complexes characterization and catalytic studies were presented.Mono- or dibromomethylarens (A-E) have been used to alkylate pyrazole (R=H) and 3,5-dimethyl pyrazole to obtain L1-5. These pyrazolylmethylarenes displaced the p-cymene of [RuCl2(p-cymene)]2 to afford monomeric and neutral pyrazole-functionalyzed arene ruthenium(II) complexes [Ru]L1-5. The bromomethylarenes (A-E), the derived pyrazolylmethylarenes L1-5. and the resulting arenerythenium(II) complexes [Ru]L1-5. have been shown in Scheme IShemeThe new Ru(II)-pyrazole functionalized arene complexes [Ru]L1-5 have been employed as catalyst for the transfer hydrogenation of acetophenone in the presence of KOH using 2-propanol as a hydrogen source and results were compared. The best result (100% yield in 6 h) in the transfer hydrogenation of acetophenone with [Ru]L2a were obtained.Keywords: Arene ruthenium(II) complexes, pyrazole, half-sandwich (piano-stool) complexes, transfer hydrogenation.
Bu tez pirazol sübstitüye aren rutenyum bileşikleriyle ilgilidir. Aren metal kompleksleri 40 yılı aşkın bir süredir araştırılmaktadır. Organometalik kimyada aren rutenyum komplekslerine artan bir ilgi vardır. h6-arene rutenyum kompleksleri içerisinde en çok çalışılanlar yarı-sandviç kompleksleridir. Bu kompleksler katalizör olarak, supramoleküler bağlanmada uygulama alanı bulmakta ve antiviral, antibiyotik ve antikanser aktivite göstermektedir. Karbon-hidrojen bağ aktivasyonu için kullanılan reaktif aren metal hidrür ara ürünlerine ulaşmak için iyi birer başlangıç maddesi olarak görülürler.Tez üç bölümden oluşmaktadır. Birinci bölümde aren rutenyum kompleksleri hazırlanışı ve türleri özetlenmiştir. Tezin ikinci bölümünde deneysel çalışmalara yer verilmiştir. Üçüncü bölümünde ise, sentezlenen aren rutenyum komplekslerinin karakterizasyonu ve katalitik incelemeler sunulmuştur.Önce, pirazol ile bromo metil benzen türevleri kullanılarak yeni ligantlar (L1-5) sentezlendi. Bu yeni pirazol türevi ligantlarla [Ru(p-simen)Cl2]2 dimeri etkileştirildi, klor köprüleri bölünerek, ligant N üzerinden rutenyuma koordine olup ve p-simen halkasının uzaklaşmasıyla, ligant aren halkasından rutenyum üzerine şapkalanarak yeni nötral kompleksler ([Ru]L1-5)sentezlendi. Sentez işlemleri Şema I'de özetlenmiştir.ŞemaSentezlenen bu yeni kompleksler [Ru]L1-5 asetofenonun transfer hidrojenasyonunda katalizör olarak test edildi: Asetofenonun transfer hidrojenasyonunda [Ru]L2a ile en iyi sonuç (6 saatte %100 verim) elde edildi.Anahtar kelimeler: aren rutenyum(II) kompleksleri, pirazol, yarı-sandviç kompleksleri, transfer hidrojenasyon.
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transfer hidrojenasyon, Kimya A.B.D., pirazol, Arene ruthenium(II) complexes, Kimya, Ruthenium, Catalytic activity, pyrazole, yarı-sandviç kompleksleri, Chemistry, half-sandwich (piano-stool) complexes, transfer hydrogenation, Catalytic hydrogenation, Aren rutenyum(II) kompleksleri
transfer hidrojenasyon, Kimya A.B.D., pirazol, Arene ruthenium(II) complexes, Kimya, Ruthenium, Catalytic activity, pyrazole, yarı-sandviç kompleksleri, Chemistry, half-sandwich (piano-stool) complexes, transfer hydrogenation, Catalytic hydrogenation, Aren rutenyum(II) kompleksleri
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