Catalytic Phosphite Hydrolysis under Neutral Reaction Conditions

Abstract

Cationic phosphametallocene-based platinum(II) aqua complexes were used as efficient precatalysts for the hydrolysis of aromatic and aliphatic tertiary phosphites under neutral reaction conditions at room temperature, leading to the selective cleavage of one P-O bond of the phosphite. NMR labeling experiments combined with stoichiometric model reactions and theoretical density functional theory calculations, performed with the appropriate model compounds, shed light on the operative catalytic cycle, which comprises intramolecular water molecule transfer to the cis-coordinated phosphite molecule.

A fluorinated phosphite traps alkoxy radicals photogenerated at the air/solid interface of a nanoparticle

“…31 P NMR for 5b at δ1.30 ppm is similar with the literature value ranging between 1.08‐1.4 ppm. [ 17,59–61 ] The proton‐decoupled 31 P peaks for 3a , 3b , 3c , and 3d appeared at 130, 129, 128.7, and 128 ppm, respectively, agreed well with (±)0.04 – (±)1.0 ppm values that were previously reported. 53 Peaks at 2.60, 1.94, and 1.36 ppm were assigned to aryl hydrogen phosphonates 5a , 5c , and 5d , respectively.…”

“…The proposed mechanism is similar to previous reports on phosphite hydrolysis. [ 17,18 ] The hydrolysis is thought to proceed through the diaryl phosphinic acid and cease at aryl hydrogen phosphonate yielding two equivalents of the p ‐substituted phenol. The reaction does not continue further to produce phosphoric acid and a third mole of p ‐substituted phenol.…”

Effects of Substitution Pattern in Phosphite Ligands Used in Rhodium-Catalyzed Hydroformylation on Reactivity and Hydrolysis Stability

“…For example, the hydrolysis stability of several bulky phosphites bearing tert-butyl groups (e.g., Alkanox P-24, Ultranox U641, Alkanox 240) used in polymer chemistry as antioxidants was investigated by the research group, by the research group of Edge [22]. Recently, Oberhauser and Manca reported on the catalytic hydrolysis of aromatic and aliphatic tertiary phosphites by cationic phosphametallocene-based platinum (II) aqua complexes under neutral reaction conditions [23]. Evidence was given that the selective cleavage of a P-O bond occurs in the coordination sphere of the platinum (II) due to the transfer of a water molecule to the phosphite.…”

Complexes of Ni(II) with triphosphine‐phosphite ligand P(OCH2PPh2)3: syntheses, structures, and electronic properties

“…A plausible explanation for this transformation is the hydrolysis of the P-O bond in P(OCH 2 PPh 2 ) 3 . [27] Such reactivity distinguishes ligand 1 from known PP 3 ligands where the bridgehead phosphorus and peripheral -PR 2 groups are connected by all-carbon (À CÀ CÀ ) linkers. It also offers new potential routes towards developing other new chelating ligands incorporating O-anionic phosphite sites.…”

“…Reactions of 1 with nickel(II) acetate, nitrate, or tetrafluoroborate proceeded differently, with the main product isolated in these reactions being complex 4 (Figure 1). A plausible explanation for this transformation is the hydrolysis of the P‐O bond in P(OCH 2 PPh 2 ) 3 [27] . Such reactivity distinguishes ligand 1 from known PP 3 ligands where the bridgehead phosphorus and peripheral ‐PR 2 groups are connected by all‐carbon (−C−C−) linkers.…”