N-functionalised heterocyclic carbene complexes and their catalytic properties

Son yirmi yılda N-heterosiklik karben (NHC) ligandları hem organometalik kimyada hem de homojen katalizde oldukça popüler hale gelmiştir. Ligand olarak kullanılan NHC'lerin çoğu imidazol çekirdeği temelli iken; kaynaşmış altı- ve yedi-üyeli kiral bisiklik iskeletli analogları, daha büyük sterik engel ve özellikle artan bazikliğe/nükleofilliğe bağlı olarak beş-üyeli türevlerden çok farklı özellikler gösterdiklerinden dolayı oldukça ilgi çekmektedirler. Sodyum azid ile kamforik asidin Schmidt Reaksiyonu yoluyla oluşturduğu (1R,3S)-diamino-1,2,2-trimetilsiklopentan'dan türeyen (1, R,S-tmcp) NHC öncüllerinin sentezi için iki yöntem vardır. İlk yöntem, başlangıçta azot atomlarının alkillenmesi ile gerçekleşen diaminin modifikasyonu ve sonrasında halka kapanmasını içerir. İkinci yöntem ise başlangıçta halka kapanması ve ardından azot atomlarının alkilasyonunu içerir. Son olarak yeni PEPPSI-tip kiral paladyum kompleksleri (9a-f), öncül kiral azolyum tuzlarının piridin varlığında, PdCl2 ve K2CO3 ile ısıtılmasıyla hazırlanmış ve 9a bileşiğinin Asimetrik Suzuki-Miyaura Çapraz-Eşleşme reaksiyonu ve Asimetrik Allilik Alkilasyon reaksiyonundaki katalitik aktivitesi incelenmiştir. Sentezlenen yeni bileşiklerin yapıları spektroskopik yöntemlerle aydınlatılmış, ayrıca 7, 9a, 9b, 9d ve 9e'nin kristal yapıları X-ışını kırınımı yöntemi ile de belirlenmiştir. N-heterocyclic carbene (NHC) ligands become increasingly popular in both organometallic chemistry and homogeneous catalysis over the past 20 years. While the majority of NHCs employed as ligands are based on an imidazole core, analogues with fused six- and seven-membered a chiral bicyclic skeleton has attracted attention, as it has been established that they possess quite different properties from the five-membered derivatives, most notably an enhanced basicity/nucleophilicity and greater steric demand. There are two main synthetic routes to bicyclic NHC precursors, which are derived from camphoric acid via a Schmidt reaction with sodium azide yielding (1R,2S)-diamino-1,2,2-trimethylcyclopentane (1, R,S-tmcp). The first route involves the initial modification of the diamine through alkylation of the nitrogen proceeded by ring closure. The second involves an initial ring closure and subsequent introduction of the exo N-alkylation. Finally, the novel PEPPSI-type chiral palladium complexes (9a-f) have been prepared by heating their precursor chiral azolium salts with PdCl2 and K2CO3 in neat pyridine and examined complex of 9a catalytic activity in the Asymmetric Suzuki-Miyaura cross-coupling reaction and Asymmetric Allylic Alkylation reaction. The structure of synthesized the novel compounds were characterized using spectroscopic techniques; also the single crystal structures of 7, 9a, 9b, 9d and 9e were determined by X-ray analysis

Synthesis of new aminodiborane(4) derivatives and characterization

Bu çalışmada yeni aminodiboran(4) bileşikleri sentezlenip ve karakterize edilmiştir. Aminodiboran(4) bileşikleri, 1,2-bis-dikloro–1,2-bis-dimetilaminodiboran ve 1,2-bisdikloro– 1,2-bis-didurildiboranın çeşitli lityumamidler ile reaksiyonuyla sentezlenmiştir. Lityumamid türevleri olarak fenilamin (anilin) ve 2,4,6- trimetilfenilamin (mezitilanilin) seçilmiştir. Fenilamin ve 2,4,6-trimetilfenilamin 2 eşdeğer n-butillityum kullanılarak aminin lityum tuzlarına dönüştürülmüştür. Aminodiboran(4) bileşikleri 2 eşdeğer n-butillityum kullanılarak dilityum diborat(4) tuzlarına dönüştürülmüştür. Dilityum diborat(4) tuzlarının diklordimetilsilan, dimetilkalay diklorid ve diklorfenilboranla etkileştirilmesiyle bor heterosiklikleri sentezlendi. Diboran(4) bileşikleri, lityumamidler ve diboran(4)’ün dilityum tuzlarının havaya ve neme karşı çok hassas olmalarından dolayı tüm deneysel çalışmalar argon atmosferi altında Schlenk tekniği kullanılarak yapılmıştır. Bütün bileşiklerinin karakterizasyonu Nükleer Manyetik Rezonans Spektroskopisi (NMR) analizi ile yapılmıştır.In this study has been prepared and characterized new aminodiborane(4) compounds. Aminodiborane(4) compounds have been prepared from reaction of 1,2-bis-dichloro– 1,2-bis-dimethylaminodiboran and 1,2-bis-dichloro–1,2-bis-diduriyldiboran with different lithiumamides. Phenylamine (aniline) and 2,4,6-trimethylphenylamine (mesitylaniline) were selected as lithiumamides derivatives. Phenylamine and 2,4,6- trimethylphenylamine were converted to lithium salts of amine using 2 equiv of nbuthylithium. Aminodiborane(4) compounds were converted to dilithium salts of diborane(4) using 2 equiv of n-buthylithium. Boron heterocycles were prepared by reacting diborate(4) dilithium salts with dichlorodimethylsilane, dimethyltin dichloride and dichlorophenylborane. Due to diborane(4) compounds, lithiumamides and dilithium salts of diborane(4) which have more sensetive of air and moisture, all experimental works were performed by using Schlenk techniques under argon atmosphere. Structural characterization of all compounds were made with Nuclear Magnetic Resonance Spectroscopy (NMR) analiysi

Synthesis of aminoboranes and heterocyclic boron compounds

Compounds featuring main group elements within the nitrogen-containing heterocyclic framework have been attracted both as reactive entities in their own right, and as potential two electron donor ligands towards transition metals. While this field has been dominated by N-heterocyclic carbenes (NHC), there have been extensive efforts to isolate and characterize the isovalent p-block analogues ofcarbene. In this way, N,N-chelated ligands containing boron heterocycles are more important compounds. In this thesis, a series of novel amidinate and β-diketiminatehaloboryl complexes were synthesized as precursor of iron complexes containing four and six membered N-heterocyclic boron analogue of carbene. The iron complexes, which containing four and six membered N-heterocyclic boron, were synthesized by the abstraction of halide from the corresponding haloboryl by Na[BArF4]. The synthesized complexes were characterized by IR, MS, NMR, X-ray and DFT techniques.Azot atomu içeren ana grup elementlerinin heterosiklik yapıları hem sahip oldukları reaktifliklerden hem de geçis metallerine karşı potansiyel iki elektron sunan ligandlar olmalarından dolayı dikkat çekmektedir. Bu alan N-heterosiklik karbenler (NHC) tarafından domine edilmesinden dolayı ana grup elementlerinin izovalent p-bloğu karben analoglarının sentezi ve karakterizasyonu için yoğun bir çaba bulunmaktadır. Bu yönü ile N,N-şelat ligandlı bor heterosiklikleri oldukça önemli bileşiklerdir. Bu tezde, dört ve altı üyeli karben analoğu N-heterosiklik bor ligandı içeren demir komplekslerinin öncülleri olarak bir seri yeni amidinat ve β-diketiminathaloboril komplekesleri sentezlenmiştir. Dört ve altı üyeli N-heterosiklik bor ligandı içeren demir kompleksleri uygun haloborillerden halojen atomunun Na[BArF4] ile uzaklaştırılması ile sentezlenmiştir. Sentezlenen kompleksler IR, MS, NMR, X-ışını kırınım ve DFT teknikleri ile karakterize edilmiştir

The Possible Interconnectedness of Religious Populism, Stigmatization, Dehumanization and Hate Crimes and an Evaluation on Muslims in Russia

Populist indoctrinations have been influencing peoples and shaping global and glocal policies for a very long time. But nowadays, the effects of populism increasingly play crucial roles in domestic policies and international relations. This research focuses on religious populism, stigmatization, dehumanization, hate crimes and violations of human rights. As a result of this research, it is suggested that there is possible interconnectedness between these phenomena. This possible interconnectedness increases the importance of these phenomena, since even the most basic violations of rights may result in creation of grave human right violations. It is reminded that religious populism indoctrinations may even lead to grave consequences like societal sterilization or crimes against humanity. Besides, the rights of Muslims living in Russia and some arguments about the contemporary conditions that they live in are examined. Finally, the importance of information and perception operations and related strategies emphasized

Synthesis, Experimental and Theoretical Characterization of (μ4-oxo)hexakis(μ2-chloro)-tetrakis[1-(allyl)-1H-imidazole]tetracopper(II)

A new [Cu4OCl6L4] cluster [L = 1-(allyl)-1H-imidazole] has been isolated and its crystal structure and spectroscopic properties determined. The compound crystallizes as a yellow solid in the monoclinic system, space group P21, with cell constants a = 10.6937(7) Å, b = 13.1004(7) Å, c = 13.2452(9) Å, β = 93.537(6)°, and two formula units per cell. The title tetranuclear complex has a central µ4-oxide ion surrounded tetrahedrally by four CuII atoms. Each Cu atom is connected to three others via bridging Cl atoms. The fifth coordination position, located on the central Cu─O axis on the outside of the cluster, is occupied by an N atom of the monodentate imidazole ligand. The resulting coordination geometry of the metal ion is a slightly distorted trigonal bipyramid with the O and N atoms in the axial positions. The molecular structure and spectroscopic data were obtained using density functional theory (DFT/HSEH1PBE) method with the cc-pVDZ basis set for C, H, N, O and Cl atoms, and the LANL2DZ basis set for the Cu atoms, and compared with the experimental data. Consequently, the experimental data well coherences with the theoretical ones

Psychological Resilience and Positivity as Predictors of Self-Efficacy

The purpose of this study is to examine the relationship between self-efficacy, a concept that has an important role in human life, and different demographic variables and the predictive roles of psychological resilience and positivity on self- efficacy. The research was carried out with 844 students studying at four different universities in provinces of Istanbul, Samsun, Bursa and Ankara in Turkey. Participants completed the questionnaire packet including the General Self-Efficacy Scale, the Brief Psychological Resilience Scale, the Positivity Scale and a personal information form. The analyses of the data were carried out via SPSS 20. The results showed that the female subjects tended to report lower self-efficacy than the males and participants living in cities and high income participants reported higher self-efficacy than the participants living in villages or small towns and the low income participants. Additionally, it may be stated that the participants who perceived their parents as democratic, negligent and protective reported higher levels of self-efficacy than those who perceived their parents as authoritarian. The results also indicated a moderate positive relationship between psychological resilience and self-efficacy, and a low positive correlation between self-efficacy and positivity. Psychological resilience and positivity were found to be important predictors of self-efficacy

Unsymmetrically substituted imidazolium salts: synthesis, characterization and antimicrobial activity

Unsymmetrically substituted imidazolium salts were synthesized and characterized using 1H-NMR and 13C-NMR. The antimicrobial activities of the salts were evaluated using the agar-well diffusion method against 14 bacteria and five yeasts. The minimal inhibitory concentrations (MIC) against seven bacteria and one yeast were also determined. Among the test compounds applied, 1, 2, 3, 6 and 11 showed activities against Micrococcus luteus ATCC 9341, Staphylococcus aureus ATCC 25923, Staphylococcus epidermidis ATCC 12228, Bacilllus cereus ATCC 11778, Bacillus subtilis ATCC 6633, Bacillus thuringiensis, Listeria monocytogenes ATCC 19112 and Candida trophicalis. However, compounds 1, 2 and 3 showed the highest antimicrobial activities against Micrococcus luteus ATCC 9341, Stapylococcus aureus ATCC 25923, Staphylococcus epidermidis ATCC 12228, Bacilllus cereus ATCC 11778 and Bacillus subtilis ATCC 6633 with inhibition zones of 14-20 mm. In addition, compound 6 have only demonstrated activities against Candida trophicalis while compounds 4, 5, 7, 8, 9, 10, 12, 13 and 14 had no effect on test microorganisms

The rises of conservative ideology in Turkey of 1994 local election of effect

YÖK Tez ID: 440117Bilindiği gibi muhafazakârlık kavramı, modernitenin yaratısı olarak değerlendirilebilmektedir. Çünkü, modernleşme, Batıda bilimsel arayışlar sonucu ortaya çıkan; toplumsal, siyasal, yönetsel ve daha birçok alanda başlı başına bir dönüşümü ifade etmek için kullanılan bir kavramdır. Bu arayışların sonucu Fransız ve Sanayii Devrimleri yaşanmıştır. Fransız Devrimi, milliyetçi söylemlerin dünyaya yayılmasına sebep olurken Sanayii Devrimi ise çeşitli siyasal, sosyal sınıf ve kutuplaşmaları doğurmuştur. Bütün bu yaşananlar sonucunda siyaset terminolojisinde yer alan üç büyük ideoloji ortaya çıkmıştır. Bunlar; muhafazakârlık, liberalizm ve sosyalizmdir. Çalışmamızın "Teorik ve Kavramsal Çerçeve" isimli ilk bölümünde, muhafazakârlığın ortaya çıkışındaki süreç tartışılmıştır. Ardından tezimizin "Türk Muhafazakârlığının Siyasal Temelleri" başlıklı ikinci bölümünde esas konumuza ışık tutması açısından muhafazakârlığın Türk siyasal hayatındaki yeri, ilk bölüm de referans alınarak, kendine özgü tarihsel birikimi çerçevesinde tartışılmıştır. Tezimizin bu ilk iki bölümünde ortaya koyduğumuz veriler ışığında, Türkiye'de muhafazakâr ideolojinin yükselişinde 1994 yerel seçimleri ve bu seçimlerde RP nin elde ettiği seçim neticesinin önemli bir kilometre taşı olduğunu iddia ettik. Çünkü bu dönemde, seçim öncesi, kulislerde kendisine fazlaca şans verilmemiş ve bu nedenle de çok fazla tartışılmamış olan RP nin, seçimden sonra aldığı sonuçlar "şoke edici" olarak yorumlanırken bir anda RP ni ana tartışma konusu yapmıştır. Bunun nedeni, RP nin başta büyükşehirler olmak üzere pek çok belediye seçimini kazanmış olması ve Doğu, Güneydoğu'da yükselen bir profil göstermesi olmuştur. Bu olay daha sonrasında önce RP ni hükümet ortağı yapmış akabinde ise RP nin içerisinden gelenler AK Partiyi kurarak 3 Kasım 2002 seçimlerinde tek başlarına iktidar olmuşlar ve on iki yıl boyunca da bu iktidarlarını sürdürmeyi başarmışlardır. Anahtar Kelimeler: Muhafazakârlık, Modernleşme, Türk Muhafazakârlığı, 1994 Yerel Seçimleri, RP, AK PartiThe concept of conservatism, as known, is evaluated as creation of modernity. Because, modernization is a concept which emerged from the results of scientific search in the West; representing a convertion itself in many areas like social, political, administrative. As a result of this search, French and Industrial revolutions have occured. As French revolution has caused the spread of nationalist expression to the World, Industrial revolution brought about many classification and polarization which is social and political. As a result of all this happened, three major ideology came out in political terminology, which is that Conservatism, Liberalism and Socialism. The firts part of our work which is called as "Theorical and Conceptual Framework", the process in the emergence of conservatism was discussed. Then, to shed light on the basis subject in the second part of our work which is titled as "Political Foundations of Turkish Conservatism", position of conservatism in Turkish political life with reference to the first part was discussed as spesific historical background frame. Through the data we revealed in these 2 part, we claimed that 1994 local election and the election results achieved by RP in this election is a milestone in the rise of conservative ideolgy. Because RP was not given much chance in the lobby before the election and therefore RP which was not much discussed became main discussion topic after the election while the results of election RP gained was interpreting as "shocking". This is because RP gained many municipal elections including especially metropolitans and demonstrated increasing profile in the East and Southeast. First this fact made RP partner in the government, some inside RP established AK Party afterwards. This party, AK Party came to power on 3 November, 2002 and managed to keep this status for 12 years. Keywords: Conservatism, Modernization, Turkish Conservatism, 1994 local election, RP, AK Part

Traces of Social-Cultural Change in Halide Edip Adıvar’s “Tatarcık” Novel / HALİDE EDİP ADIVAR’IN “TATARCIK”* ROMANINDA SOSYAL/KÜLTÜREL DEĞİŞMENİN İZLERİ

Halide Edip Adıvar, in her Tatarcık novel that she tackles social change and modernization problems, examines alienation as a consequence of Westernization. Tatarcık novel has been serialized in Yedigün journal for the first time in 1939, and then has been published several times. In 1968, the novel was reprinted as a simplified copy. Tatarcık novel, in this study, is analysed in terms of the characteristics of the individual and social change of republic period and is qualitatively evaluated. To this end, firstly the life and works of Halide Edip Adıvar are briefly introduced and secondly the traces of social/cultural change is debated. Blended with the literary style, there are various indicators of social and cultural change which are examined in the novel such as values and the value judgements, manners of life, material and moral acceptances and aspects on all these have changed after the establishment of the republic. In this study, similarly looking at the traces of social/cultural change in the context of modernization/westernization, observations on change dynamics, religious values, education, view on women, European style culture, cultural degeneration themes are debated. It is concluded that novel characters who play a role of carriers of social problems are two folds, whereas one group believe in formal and the other refers to essential modernisation. Furthermore, it is important to note that the social problems narrated in the novel are rooted in the transitional characteristics of the period. Even though Tatarcık character is far from directly representing the women of the era, in this transition period Tatarcık concretizes as a synthesis of East and West. In this context, it could be thought that she represents the ideal of westernization itself