2018年9月4日以色列理工学院Graham de Ruiter教授学术报告

Metal-Metal and Metal-Ligand Cooperation for Activating Small Molecules: Unprecedented Rate Acceleration for Oxygen Atom Transfer

发布人:高级管理员 发布日期:2018-09-03
主题
Metal-Metal and Metal-Ligand Cooperation for Activating Small Molecules: Unprecedented Rate Acceleration for Oxygen Atom Transfer
活动时间
-
活动地址
丰盛堂A403
主讲人
Graham de Ruiter教授
主持人
韩治际教授

报告主题:Metal-Metal and Metal-Ligand Cooperation for Activating Small Molecules: Unprecedented Rate Acceleration for Oxygen Atom Transfer

报告人:Graham de Ruiter教授 以色列理工学院(Technion - Israel Institute of Technology)

主持人:韩治际教授

时间:2018年9月4日16:00-17:00

地点:丰盛堂A403

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报告摘要:

The versatility by which iron-containing metalloenzymes are able to activate and oxygenate C–H bonds with molecular oxygen has sparked much interest in the underlying mechanism. It has been shown that high-valent iron metal centers bearing terminal metal-oxo motifs are commonly invoked in the oxygenation step, and their formation has been studied in many monometallic iron model complexes. Despite the intense research efforts, terminal metal-oxo motifs on multi-metallic scaffolds are rare. Recently, we presented a new class of tetra-iron complexes that are site differentiated. In these complexes, three six-coordinate iron centers form a trimetallic “core” that is connected to a fourth unique coordinatively unsaturated apical iron center. We have also shown that treating – for example – [LFe3(PhPz) 3OFe] [OTf] 2(PhPz = Ph pyrazolate) with oxygen-atom transfer reagents results in regioselective intramolecular hydroxylation of an arene C–H bond. These reactivity patterns suggest the involvement of a rare FeIV-oxo motif on well-defined multi-metallic scaffold. Here we show that the selectivity and reactivity of the different metal clusters can be modulated by regulating the oxidation state of the trimetallic “core” resulting in intramolecular electron transfer pathways that are able to alter the reactivity of terminal iron-oxo species (e.g. MIV-O vs. MIII-O), and unprecedented rate acceleration in oxygen atom transfer reactions.

 

报告人简介:

Graham attended Leiden University where he received his Bachelor (B.Sc.) and Master (M.Sc.) degree (cum laude) under the supervision of Prof. Jan Reedijk. In 2008, Graham returned to the Weizmann Institute Science to pursue his Ph.D. studies with Prof. Milko E. van der Boom, working on sequence dependent assembly strategies and molecular logic. After obtaining his Ph.D., Graham moved to the California Institute of Technology to work with Prof. Theodor Agapie on the synthesis of multi-metallic complexes for small molecule activation and oxygen atom transfer reactions. Graham returned to Israel in 2017 as a Horev Fellow to start his independent career at the Technion - Israel Institute of Technology (Haifa). During his studies, Graham has received the Israel Chemical Society (ICS) Award for excellent graduate student (2011), the International Precious Metal Institute (IPMI) Sabin Metal Corporation Student Award (2013), the Feinberg Graduate School (FGS) Dimitris N. Chorafas Prize (2013), and the Azrieli Fellowship (2017).

 

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