Synthesis and Reactivity of 2-Aminophenylpalladium(II) Complexes: Insertion Reactions of Oxygen and Carbon Monoxide into Carbon−Palladium Bonds—New Examples of “Transphobia”

Abstract

Abstract:Mixtures of ªPd(dba) 2 º (dba dibenzylideneacetone) and neutral ligands react with an excess of 2-iodoaniline to give [Pd(C 6 H 4 NH 2 -2)-

New cationic palladium (II) and rhodium (I) complexes of [Ph2PCH2C(Ph)N(2,6-Me2C6H3)]

“…The relative cis-arrangement of the phosphines was found in [Rh(L) 2 ][BF 4 ] (4). These observations are also consistent with previous literature reports, which suggested that the mutual trans positioning (in square planar complexes) of two phosphorous ligands, or of a phosphorus and a carbon ligand, would lead to the weakening of the corresponding M-P bonds[71,82].…”

Rate and Mechanism of the Oxidative Addition of Benzoic Anhydride to Palladium(0) Complexes in DMF

“…[13,14] A second ionic species is then generated in a subsequent reaction. This latter might be a decarbonylation as in Equation (10) or any decomposition process leading to more conductive ionic species {e.g., formation of a phosphonium salt PhCOO-PPh 3 ϩ via a reductive elimination from [(PhCO)Pd(OCOPh)(PPh 3 ) 2 ], [15] reaction of dioxygen with [(PhCO)PdS(PPh 3 ) 2 ] ϩ , [16] etc.}. …”

“…Consequently, one equiv. (16)]. [24] Such a complex did not appear when PPh 3 was exchanged by dppp in Scheme 1.…”

Synthesis and Structure of an Asymmetric Binuclear Phenylhydrazonato Anionic Complex of Palladium Containing a Pd−C(aryl) Bondcis to a Pd−N(amido) Bond

“…Arylpalladium complexes tend to coordinate hard ligands in a position trans to the PdϪC(aryl) bond and to avoid coordination of soft ligands. This fact has been reported as transphobia, [14,15] and is followed in trans-[PdAr(NHPh)(PMe 3 ) 2 ]. [8] In complex 1 the hard N(amido) ligand arranges cis to the PdϪC(aryl) bond, leaving the softer ligand chloro in trans position to the PdϪC(aryl) bond.…”