Hacimli benzil grubu içeren diaminokarben komplekslerinin sentezi ve özellikleri
Küçük Resim Yok
Tarih
2001
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Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
İnönü Üniversitesi
Erişim Hakkı
info:eu-repo/semantics/closedAccess
Özet
ÖZET Yüksek Lisans Tezi HACİMLİ BENZİL GRUBU İÇEREN DİAMİNOKARBEN KOMPLEKSLERİNİN SENTEZİ VE ÖZELLİKLERİ Serpil DEMİR İnönü Üniversitesi Fen Bilimleri Enstitüsü Kimya Anabilim Dalı xi + 74 sayfa 2001 Tez Danışmanı: Yrd.Doç.Dr.İsmail ÖZDEMİR Karben kompleksleri, L"M=CXY, üzerindeki çalışmalar son yıllarda hızlı bir gelişme göstermiştir ve pek çok karben kompleksi sentezlenmiştir. Fakat hacimli ve işlevsel grup içeren JV-heterosiklik karben kompleksleri üzerinde yeterince çalışılmamıştır. Bu çalışmanın amacı, sözkonusu boşluğu doldurmak ve sentezlenen bileşiklerin katalitik özelliklerini incelemektir. Burada üç yeni tetraamindalken (2a-c) ve bunlardan türeyen altı yeni karben kompleksi sentez ve karakterize (3 ve 6 tek kristal X-ışınlan ile) edilmiştir. N üzerinde hacimli benzil (mesitilbenzil) içeren 2a olefini [RuCİ2(p-simen)]2 ve [RuCİ2(HMB)]2 bileşikleriyle etkileştirildiğinde p-simen ve hekzametilbenzen grubu rutenyum metalini terk ederek 2,4,6-trimetilbenzil grubundan bir tanesi aren üzerinden metale koordine olmakta diğeri ise serbest kalmaktadır. Kelat oluşturmanın hangi koşullara bağlı olduğunu belirlemek amacıyla 2b ve 2c bileşikleri ve onlardan türeyen karben kompleksleri hazırlanmıştır. 2b bileşiği [RuCİ2(/?-simen)]2 ile etkileştiğinde /7-simen grubu rutenyu ederek 5 kompleksi oluşurken aynı olefin [RuCİ2(HMB)]2 ile 6 [RuCfeı kompleksini oluşturur. Bu 6 nolu bileşik 140 °C de ısıtıldığında HMB grubu rutenyumu terk ederek yine 5 nolu kompleks elde edilmektedir. Oysa, benzil içeren 2c, kelat yapı yerine beklenen karben komplekslerini (7 ve 8) vermiştir. I I CN N- i N N- ' ı l « R' 2 a R=CH2Mes; R'-CfyMes bR-CtyCfyOCH,; K=CH2Mes c R=CH2CH20CH3; R* = CH2Ph \ r c N Cl / CH,0 CH,0 CH,0 7 ı-N /T\ [ >-* I- N Cl CI OTf 9: R = CH2CH2OCH3 10: R=2,4,6-(CH3)3C6H2CH2 crço Sentezlenen kompleksler (3 ve 5) yeni rutenyum-aleniliden komplekslerine (9 ve 10) dönüştürülmüş ve bunların bazılarının dien siklik izomerizasyonunda ve halka kapanma metatez tepkimelerinde aktif katalizörler olduğu saptanmıştır. ANAHTAR KELİMELER: N-heterosiklik karben, rutenyum ve rodyum komple olefin metatezi, sildik izomerizasyon. ıı
ABSTRACT Master Thesis SYNTHESIS OF BULKY DIAMNOCARBENE COMPLEXES AND THEIR PROPERTIES Serpil DEMİR inönü University Graduate of Natural and Applied Sciences Department of Chemistry xi + 74 pages 2001 Supervisor: Assis. Prof.Dr. Ismail Özdemir Carbene based complexes and it's derivatives have been extensively studied and utilized for the past two decades. However, bulky and functional group containing N- heterocylic carbene complexes has yet to be studied. The aim of this work is to study to fulfill the this gap and to investigate the catalytic activity of prepared complexes. Here, we report the synthesis of three novel tetraaminoalkenes ( 2a-c) and six new compounds derived from them and their characterization ( 3 and 6 single crystal via x-ray diffraction pattern ). When 2a olefine that contains bulky N- substituted mesitylbenzyl interacted with [RuCİ2(/?-cymene)]2 and [RuCİ2(HMB)J2, /?-cymene and hexamethylbenzene left ruthenium metal and coordinated to metal via one of the 2,4,6- timethylbenzyl groups as a results one of the groups remains free. In order to determine the chelation mechanism and figure out to chelation conditions complex 2b and 2c and complexes derived from them were prepared. When 2b complex interacted with [RuCİ2(^-cymene)]2, p-cymene a group left the metal and as a result complex 5 was formed, the same olefin formed 6 complex with [RuCİ2(HMB)]2. This complex,6, when heated to 140 °C, has led the formation of complex 5, due to HMB group left the metal. On the contrary, benzyl containing olefin 2c, gave expected carbene complexes ( 7, and 8) instead of chelate structure. I I EN N- i N N-J i i R" R' 2 EN ' >-* N VC1 < \ J a R=CH2Ma; R^CHîMes b R'CHjCHjOCHî; R'-CHjMes cR-CHsCHîOCH,; R'=CH2Ph 1 / r"N ' JS^ CH,0 CH,0 LN"c. I- N CI CI OTf 9: R=CH2CH2OCH3 10: R^ZiMCHihCJiiCHi Thus prepared complexes ( 3 and 5) has transformed to the novel ruthenium- allenylidene complexes ( 9 and 10) and it has been found that some of the complexes act as active catalyts in ring closure metathesis reactions and in diene cyclic isomerization. Key words: N-heterocyclic carbene, Ruthenium and rhodium complexes, olefin metathesis, cyclic isomerization. IV
ABSTRACT Master Thesis SYNTHESIS OF BULKY DIAMNOCARBENE COMPLEXES AND THEIR PROPERTIES Serpil DEMİR inönü University Graduate of Natural and Applied Sciences Department of Chemistry xi + 74 pages 2001 Supervisor: Assis. Prof.Dr. Ismail Özdemir Carbene based complexes and it's derivatives have been extensively studied and utilized for the past two decades. However, bulky and functional group containing N- heterocylic carbene complexes has yet to be studied. The aim of this work is to study to fulfill the this gap and to investigate the catalytic activity of prepared complexes. Here, we report the synthesis of three novel tetraaminoalkenes ( 2a-c) and six new compounds derived from them and their characterization ( 3 and 6 single crystal via x-ray diffraction pattern ). When 2a olefine that contains bulky N- substituted mesitylbenzyl interacted with [RuCİ2(/?-cymene)]2 and [RuCİ2(HMB)J2, /?-cymene and hexamethylbenzene left ruthenium metal and coordinated to metal via one of the 2,4,6- timethylbenzyl groups as a results one of the groups remains free. In order to determine the chelation mechanism and figure out to chelation conditions complex 2b and 2c and complexes derived from them were prepared. When 2b complex interacted with [RuCİ2(^-cymene)]2, p-cymene a group left the metal and as a result complex 5 was formed, the same olefin formed 6 complex with [RuCİ2(HMB)]2. This complex,6, when heated to 140 °C, has led the formation of complex 5, due to HMB group left the metal. On the contrary, benzyl containing olefin 2c, gave expected carbene complexes ( 7, and 8) instead of chelate structure. I I EN N- i N N-J i i R" R' 2 EN ' >-* N VC1 < \ J a R=CH2Ma; R^CHîMes b R'CHjCHjOCHî; R'-CHjMes cR-CHsCHîOCH,; R'=CH2Ph 1 / r"N ' JS^ CH,0 CH,0 LN"c. I- N CI CI OTf 9: R=CH2CH2OCH3 10: R^ZiMCHihCJiiCHi Thus prepared complexes ( 3 and 5) has transformed to the novel ruthenium- allenylidene complexes ( 9 and 10) and it has been found that some of the complexes act as active catalyts in ring closure metathesis reactions and in diene cyclic isomerization. Key words: N-heterocyclic carbene, Ruthenium and rhodium complexes, olefin metathesis, cyclic isomerization. IV
Açıklama
Anahtar Kelimeler
Kimya, Chemistry
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Künye
Demir, S. (2001). Hacimli benzil grubu içeren diaminokarben komplekslerinin sentezi ve özellikleri .Yayımlanmış Yüksek lisans Tezi, İnönü Üniversitesi, Malatya.
