Design, Synthesis, Characterization and Catalytic Activity in Direct Arylation Reaction of the Benzimidazole-Functionalized PEPPSI-type Pd(II)NHC Complexes bearing 4-Vynylbenzyl Group

Öz

This study includes the synthesis and characterization of a series of benzimidazole functional PEPPSI (PEPPSI, Pyridine Enhanced Precatalyst Preparation Stabilization, and Initiation) type Pd(II)NHC (NHC, N-heterocyclic Carbene) complexes containing the 4-vinylbenzyl group. These complexes were synthesized from benzimidazolium salts bearing 4-vinylbenzyl group, palladium chloride (PdCl2), potassium carbonate (K2CO3) and 3-chloropyridine as a base. The structures of all complexes were characterized using 1H NMR, 13C NMR, and FTIR spectroscopic techniques. The data obtained from characterization were consistent with the proposed formulas. In particular, the absence of characteristic proton and carbon peaks of benzimidazolium salts with 4-vinylbenzyl group used as starting material in NMR spectra, instead of the coordination of benzimidazolium ligand to palladium metal, the presence of carbene peaks in the downfield of the carbon NMR spectrum proves the formation of complexes. In addition, the catalytic activities of all PEPPSI type Pd(II)NHC complexes with benzimidazolium functionalities containing 4-vinylbenzyl groups in direct arylation reactions were investigated. All complexes used as catalysts in the responses of aryl bromides with furan and thiophene derivative compounds were found to be moderately and highly active catalysts in these reactions.

Anahtar Kelimeler

• Catalyst
• Direct arylation
• N-heterocyclic carbene
• Palladium
• PEPPSI

4-Vynilbenzil Grubu Taşıyan Benzimidazol Fonksiyonelleştirilmiş PEPPSI tipi Pd(II)NHC Komplekslerinin Dizaynı, Sentezi, Karakterizasyonu ve Doğrudan Arilasyon Reaksiyonundaki Katalitik Aktivitesi

Öz

Bu çalışma, 4-vinilbenzil grubunu içeren bir dizi benzimidazol fonksiyonelli PEPPSI (PEPPSI, Pyridine Enhanced Precatalyst Preparation Stabilization, and Initiation) tipi Pd(II)NHC (NHC, N-heterocyclic Carbene) kompleksinin sentezini ve karakterizasyonunu içerir. Bu kompleksler 4-vinilbenzil grubu taşıyan benzimidazolyum tuzları, paladyum klorür (PdCl2), baz olarak potasyum karbonat (K2CO3) ve 3-kloropiridinden sentezlendi. Tüm komplekslerin yapıları 1H NMR, 13C NMR ve FTIR spektroskopik teknikleri kullanılarak karakterize edildi. Karkterizasyon sonucu elde edilen veriler önerilen formüller ile tutarlıydı. Özellikle NMR spektrumlarında başlangıç materyali olarak kullanılan 4-vinilbenzil grubu taşıyan benzimidazolyum tuzlarına ait karakteristik proton ve karbon piklerinin gözlenmemesi, bunu yerine benzimidazolyum ligandının palladyum metaline koordinasyonu sonucu karbon NMR spektrumunda daha düşük alanda karben piklerinin varlığı komplekslerin oluşumunu kanıtlamaktadır. Ayrıca, tüm 4-vinil benzil grubu içeren benzimidazolyum fonsiyonelli PEPPSI tipi Pd(II)NHC komplekslerinin doğrudan arilasyon tepkimelerindeki katalitik aktiviteleri incelenmiştir. Aril bromürlerin, furan ve tiofen türevi bileşikler ile tepkimelerinde katalizör olarak kullanılan tüm komplekslerin bu reaksiyonlarda orta ve yüksek derecede aktif katalizörler oldukları görülmüştür.

Anahtar Kelimeler

• Doğrudan arilasyon
• Katalizör
• N-heterosiklik karben
• Palladyum
• PEPPSI

Kaynakça

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