Strong Bond Activation with Late Transition-Metal Pincer Complexes as a Foundation for Potential Catalysis
| dc.contributor | Ozerov, Oleg V. | |
| dc.creator | Zhu, Yanjun | |
| dc.date.accessioned | 2014-09-16T07:28:21Z | |
| dc.date.accessioned | 2017-04-07T20:00:23Z | |
| dc.date.available | 2014-09-16T07:28:21Z | |
| dc.date.available | 2017-04-07T20:00:23Z | |
| dc.date.created | 2012-05 | |
| dc.date.issued | 2012-07-16 | |
| dc.description.abstract | 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. | |
| dc.identifier.uri | http://hdl.handle.net/1969.1/ETD-TAMU-2012-05-10965 | |
| dc.language.iso | en_US | |
| dc.subject | bond activation | |
| dc.subject | transition-metal complxes | |
| dc.subject | C-H activation | |
| dc.subject | C-O activation | |
| dc.subject | oxidative addition | |
| dc.subject | reductive elimination | |
| dc.subject | fluorocarbyne complex | |
| dc.title | Strong Bond Activation with Late Transition-Metal Pincer Complexes as a Foundation for Potential Catalysis | |
| dc.type | Thesis |