Boryl/Borane Interconversion and Diversity of Binding Modes of Oxygenous Ligands in PBP Pincer Complexes of Rhodium uri icon

abstract

  • 2017 American Chemical Society. A series of Rh complexes derived from a PBP-type pincer ligand have been synthesized and characterized. It was previously reported that reaction of [(COD)RhCl]2 with 2,2-bis(diisopropylphino)triphenylborane (1) resulted in a mixture of complexes containing a Z-type borane interaction (2-Cl), a boryl pincer (3a-Cl), and a 2 binding of the B-Ph bond to Rh (4-Cl). In this work, we demonstrate that analogous complexes are accessible by replacement of chloride with potentially bidentate acetylacetonate, carboxylate, and trifluoromethanesulfonate ligands. In addition, a new type of isomer was observed in complexes with acetate and pivalate, where the carboxylate bridges between Rh and B (3b-OAc, 3b-OPiv). All of these types of complexes are isomeric, and the preference for particular isomers for different anionic ligands varies. These isomers differ and are related by a change in the coordination mode of the oxygenous ligands and the migration of the Ph group between B and Rh.

published proceedings

  • ORGANOMETALLICS

author list (cited authors)

  • Shih, W., Gu, W., MacInnis, M. C., Herber, D. E., & Ozerove, O. V.

citation count

  • 40

complete list of authors

  • Shih, Wei-Chun||Gu, Weixing||MacInnis, Morgan C||Herber, David E||Ozerove, Oleg V

publication date

  • May 2017