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Strong Bond Activation with Late Transition-Metal Pincer Complexes as a Foundation for Potential Catalysis

Strong 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.

Identiferoai:union.ndltd.org:tamu.edu/oai:repository.tamu.edu:1969.1/ETD-TAMU-2012-05-10965
Date2012 May 1900
CreatorsZhu, Yanjun
ContributorsOzerov, Oleg V.
Source SetsTexas A and M University
Languageen_US
Detected LanguageEnglish
Typethesis, text
Formatapplication/pdf

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