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dc.contributorOzerov, Oleg V.
dc.creatorZhu, Yanjun
dc.date.accessioned2014-09-16T07:28:21Z
dc.date.accessioned2017-04-07T20:00:23Z
dc.date.available2014-09-16T07:28:21Z
dc.date.available2017-04-07T20:00:23Z
dc.date.created2012-05
dc.date.issued2012-07-16
dc.identifier.urihttp://hdl.handle.net/1969.1/ETD-TAMU-2012-05-10965
dc.description.abstractStrong bond activation mediated by pincer ligated transiton-metal complexes has been the subject of intense study in recent years, due to its potential involvement in catalytic transformations. This dissertation has focused on the net heterolytic cleavage of B-H and B-B bonds across the N-Pd bond in a cationic (PNP)Pd fragment, the C-H oxidative addition to a (PNP)Ir center and the recent results on the C-H and C-O oxidative addition in reactions of aryl carboxylates with the (PNP)Rh fragment. Transition metal carbene and carbyne complexes are of great interest because of their role in a wide variety of catalytic reactions. Our work has resulted in the isolation of a rhodium(I) difluorocarbene. Reaction of the rhodium difluorocarbene complex with a silylium salt led to the C-F bond cleavage and the formation of a terminal fluorocarbyne complex. Reductive elimination is a critical step of cross coupling reactions. In order to examine the effect of the pincer ligand on the reductive elimination reactions from Rh(III), the first pi-accepting PNP ligand bearing pyrrolyl substituents was prepared and installed onto the rhodium center. Arylhalide (halide = Br, I) oxidative addition was achieved in the presence of donor ligands such as acetonitrile to form stable six-coordinate Rh(III) compounds. The C-O reductive elimination reactions in this system were also explored.
dc.language.isoen_US
dc.subjectbond activation
dc.subjecttransition-metal complxes
dc.subjectC-H activation
dc.subjectC-O activation
dc.subjectoxidative addition
dc.subjectreductive elimination
dc.subjectfluorocarbyne complex
dc.titleStrong Bond Activation with Late Transition-Metal Pincer Complexes as a Foundation for Potential Catalysis
dc.typeThesis


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