Structure and Reactivity of Ag(I) Complexes Bearing Tridentate Phosphinine Ligands

Abstract

Structure and reactivity of novel Ag(I) complexes with tridentate phosphinine (phosphabenzene) ligands are discussed in this article. An equilibrium between the dimer and the monomer was observed for the λ3-phosphinine Ag(I) complex in the solution state. The λ3-phosphinine Ag(I) complex can be oxidized by PhI(OAc)2 to afford λ5-phosphinine species, maintaining the coordination to the metal center. Photochemical properties of the Ag(I) complexes were also investigated, and the emission of the λ3-phosphinine Ag(I) complex showed solvatochromic behavior.

The case of a μ2-P aromatic phosphinine as a 4-electron donor forming σ- and π-three–center-two-electron bonds

“…1b). In agreement with our findings, the interactions between a π-type orbital of μ 2 -P phosphinine and Rh( i ) 4 c or Ag( i ) 19 have been suggested independently by the group of Müller and Nozaki very recently. Similar interactions in the μ 2 -P 1,3-benzazaphosphole Cu( i ) complex have also been reported.…”

“…Therefore, the μ 2 -P phosphinine binding mode is thermodynamically less stable than the η 1 -P phosphinine binding mode, and often shows experimentally the dynamic equilibrium in solution. 4 a , e ,4 f ,10,19,22 For instance, Mathey and co-workers prepared a Cu( i ) phosphinine-2-ol ( C , Fig. 1a) complex displaying both η 1 -P and μ 2 -P phosphinines in the solid state.…”

A dinuclear Rh(−i)/Rh(i) complex bridged by biphilic phosphinine ligands

“…The pincer ligand 1 was synthesized following our previous report. 46 By treating ligand 1 with [RhCl(cod)] 2 , an orange powder was obtained. The powder was insoluble in common solvents, which suggests that a bimetallic or polymetallic structure was formed in the solid.…”

“…The phosphinine ligand formed a dinuclear complex when coordinated to silver centres. 46 Here, in this report, we present syntheses and structural analysis of a dinuclear Rh(− i )/Rh( i ) complex bridged by phosphinine pincer ligands ( Fig. 2 ).…”