Polidentat karben öncüllerinin sentezi ve özellikleri
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Dosyalar
Tarih
2014
Yazarlar
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Yayıncı
İnönü Üniversitesi
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
İlk kararlı karbenin sentezini takiben N-heterosiklik karben öncülleri ve bu ligantların metal kompleksleri organometalik kimya ve katalizde etkin bir çalışma alanı oluşturmuştur. N-heterosiklik karben öncüllerinin mono ve bidentat türleri literatürde yaygın bir şekilde yer almaktadır. Bu bileşikler C-C bağ oluşum reaksiyonları, olefin metatezi, hidrosilasyon, hidroformilasyon ve C-H aktivasyonu gibi bir çok reaksiyonda kullanılmaktadır. Polidentat karben öncülleri literatürde sahip oldukları özellikler dolayısıyla son zamanlarda artan bir ilgi görmektedir. Bu N-heterosiklik karben öncülleri ve bu karben öncüllerinden sentezlenen geçiş metal kompleksleri küçük molekül aktivasyonu, C-H aktivasyonu, C-C eşleşme reaksiyonları, hidrosilasyon ve alkilasyon gibi birçok reaksiyonda yüksek katalitik aktivite göstermektedir. Ayrıca kelat etkileri, katalitik tepkimelerde istenmeyen yan ürünlerin oluşumunu engellemeleri gibi özellikleri polidentat karbenlere olan ilgiyi de arttırmıştır. Bu nedenle bu çalışmada benzimidazol ve imidazolin çekirdeği içeren tetrakis ve heksakis azolyum tuzları sentezlenmiştir. Bulunan sonuçlar dört başlıkta özetlenebilir; 1) N-sübstitüye benzimidazol ve imidazolin bileşiklerinden tetrakis ve heksakis azolyum tuzları hazırlanmıştır. Bu bileşiklerin yapıları uygun spektroskopik yöntemlerle aydınlatılmıştır. 2) Sentezlenen azolyum tuzlarının Pd(OAc)2 varlığında in situ yöntemle Suzuki tepkimesindeki katalitik aktiviteleri incelenmiştir. 3) Sentezlenen azolyum tuzlarının Pd(OAc)2 varlığında in situ yöntemle Heck tepkimesindeki katalitik aktiviteleri incelenmiştir. 4) Sentezlenen azolyum tuzlarının Pd(OAc)2 varlığında in situ yöntemle heteroaromatik türlerin arilasyonundaki katalitik aktiviteleri incelenmiştir.
Following the synthesis of the first stable carbene, N-heterocyclic carbene procursors and metal complexes of these ligands are formed an effective area on organometalic chemistry and catalysis. Mono and bidentat derivatives of N-heterocyclic carbene precursors are widespread in the literature. These complexes are used many reactions such as C-C bond formation, olefine methatesis, hydroxylation, hydroformilation and C-H aktivation. However polydentate N-heterocyclic carbene procursors and transition metal complexes which synthesed from these precursors have high catalytic efficiency in many reactions such as small molecule activation, C-H activation, C-C coupling reactions, hydrosilation and alkylation. Furtheremore chelating effects and preventing of formation of undesirable by-products in the catalytic reaction also increased interest in those carbide polydentate. Therefore tetrakis and hexakis azolium salts which contains benzimidazole and imidazoline core are synthesized in this study. The results could be summarized in four sections: 1) In the first part we discuss the tetrakis(azolium) salts and hexakis(azolium) salts from the synthesis N-substituted imidazoline and benzimidazole with 1,2,4,5-tetrakis(bromethyl)benzene and hexakis(bromomethyl)benzene. Structural investigation have been carried out with proper spectroscopic techniques. 2) Prepared azolium salts have been tested for Suzuki reaction in the presence of Pd(OAc)2, and carbenes formed in situ in the reaction media., and the catalytic activities were investigated. 3) Prepared azolium salts have been tested for Heck reaction in the presence of Pd(OAc)2, and carbenes formed in situ in the reaction media., and the catalytic activities were investigated. 4) Prepared azolium salts have been tested for arylation of heteroaryls in the presence of Pd(OAc)2, and carbenes formed in situ in the reaction media., and the catalytic activities were investigated.
Following the synthesis of the first stable carbene, N-heterocyclic carbene procursors and metal complexes of these ligands are formed an effective area on organometalic chemistry and catalysis. Mono and bidentat derivatives of N-heterocyclic carbene precursors are widespread in the literature. These complexes are used many reactions such as C-C bond formation, olefine methatesis, hydroxylation, hydroformilation and C-H aktivation. However polydentate N-heterocyclic carbene procursors and transition metal complexes which synthesed from these precursors have high catalytic efficiency in many reactions such as small molecule activation, C-H activation, C-C coupling reactions, hydrosilation and alkylation. Furtheremore chelating effects and preventing of formation of undesirable by-products in the catalytic reaction also increased interest in those carbide polydentate. Therefore tetrakis and hexakis azolium salts which contains benzimidazole and imidazoline core are synthesized in this study. The results could be summarized in four sections: 1) In the first part we discuss the tetrakis(azolium) salts and hexakis(azolium) salts from the synthesis N-substituted imidazoline and benzimidazole with 1,2,4,5-tetrakis(bromethyl)benzene and hexakis(bromomethyl)benzene. Structural investigation have been carried out with proper spectroscopic techniques. 2) Prepared azolium salts have been tested for Suzuki reaction in the presence of Pd(OAc)2, and carbenes formed in situ in the reaction media., and the catalytic activities were investigated. 3) Prepared azolium salts have been tested for Heck reaction in the presence of Pd(OAc)2, and carbenes formed in situ in the reaction media., and the catalytic activities were investigated. 4) Prepared azolium salts have been tested for arylation of heteroaryls in the presence of Pd(OAc)2, and carbenes formed in situ in the reaction media., and the catalytic activities were investigated.
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Doğan, Ö. (2014). Polidentat karben öncüllerinin sentezi ve özellikleri. İnönü Üniversitesi Fen Bilimleri Enstitüsü. 1-179 ss.
