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SUMMARY:Identification of Active Species and Mechanistic Pathways  in the 
 Enantioselective Catalysis with 3d Transition Metal Pincer Complexes - Pro
 fessor Lutz H. Gade\, Heidelburg University
DTSTART:20180227T140000Z
DTEND:20180227T150000Z
UID:TALK94498@talks.cam.ac.uk
CONTACT:Sharon Connor
DESCRIPTION:Key challenges in the development of catalysts based on first 
 row ("3d") transition metals include the substitutional lability of the op
 en shell species involved\, the changes of spin states in the individual r
 eaction steps as well as the potential competition of single electron tran
 sfer steps. Most reaction sequences involve almost exclusively paramagneti
 c catalysts and catalytic intermediates. These properties render mechanist
 ic studies challenging and also require care in the design of stereodirect
 ing ligands.\n\nRecently\, we have developed new chiral pincer (PmBOX\, Bo
 xmi\,...) ligands[1] which have been used in a variety of enantioselective
  transformations including alkylations of β-ketoesters and their subseque
 nt cyclization to spirolactones\, as well as the trifluoromethylation and 
 azidation of β-ketoesters as well as oxindoles.[2] Their iron(II) and man
 ganese(II) complexes match the activity and selectivity of the most effici
 ent noble metal catalysts for the hydrosilylation or hydroboration of keto
 nes.\n\nThe focus of the lecture will be the elucidation of the catalytic 
 reaction mechanisms\, including radical reaction networks\,[4] and the ide
 ntification and characterization of the (frequently) paramagnetic species 
 involved.\n 
LOCATION:Wolfson Lecture Theatre\,  Department of Chemistry
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