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

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 (<b>1</b>) resulted in a mixture of complexes containing a <i>Z</i>-type borane interaction (<b>2-Cl</b>), a boryl pincer (<b>3a-Cl</b>), and a η² binding of the B–Ph bond to Rh (<b>4-Cl</b>). 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 (<b>3b-OAc</b>, <b>3b-OPiv</b>). 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

Facile Insertion of Rh and Ir into a Boron–Phenyl Bond, Leading to Boryl/Bis(phosphine) PBP Pincer Complexes

The unexpectedly facile insertion of Rh or Ir into a B–Ph bond (reversible for Rh) converts a borane/bis­(phosphine) precursor into a boryl/bis­(phosphine) PBP pincer ligand. Interconversions between the boryl/borane/borate central functionality are demonstrated in reactions with dihydrogen

Facile Insertion of Rh and Ir into a Boron–Phenyl Bond, Leading to Boryl/Bis(phosphine) PBP Pincer Complexes

The unexpectedly facile insertion of Rh or Ir into a B–Ph bond (reversible for Rh) converts a borane/bis­(phosphine) precursor into a boryl/bis­(phosphine) PBP pincer ligand. Interconversions between the boryl/borane/borate central functionality are demonstrated in reactions with dihydrogen

Silyl–Silylene Interplay in Cationic PSiP Pincer Complexes of Platinum

Herein we report the synthesis and spectroscopic observation of a Pt complex featuring a P₂Si ligand containing a central silylene donor connected to phosphines via two <i>o</i>-arylene linkers. Species of the type (P₂Si)­PtR undergo a net 1,2-migration of R from Pt to Si, which leads to highly unsaturated Pt cations displaying only a very distant interaction with the weakly coordinating carborane anion

Silyl–Silylene Interplay in Cationic PSiP Pincer Complexes of Platinum

Herein we report the synthesis and spectroscopic observation of a Pt complex featuring a P₂Si ligand containing a central silylene donor connected to phosphines via two <i>o</i>-arylene linkers. Species of the type (P₂Si)­PtR undergo a net 1,2-migration of R from Pt to Si, which leads to highly unsaturated Pt cations displaying only a very distant interaction with the weakly coordinating carborane anion