A bis(arylphosphinito)amide pincer ligand that binds nickel forming six-membered metallacycles. (15th March 2020)

• Record Type: Journal Article
• Authors: Bruch, Quinton J.; Miller, Alexander J.M.
• Is Part Of: Polyhedron. Volume 179(2020)
• Publication Date: 2020-03-15
• Subjects: Pincer ligand -- Nickel -- Coordination chemistry -- Hydride -- PNP -- PONOP -- Phosphine; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2020.114380
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: A new anionic bis(arylphosphinito)amide pincer ligand, P2 ONO −, is reported. Nickel bromide and hydride complexes featuring six-membered metallacycles are prepared and assessed using steric and electronic parameters. Abstract: The synthesis of a bis(arylphosphinito)amide pincer ligand P2 ONO − designed to form two six-membered rings upon metallation is reported. Phosphination of a known bis(phenolato)amide ONO 3− scaffold led to isolation of two isomers: the intended H(P2 ONO) preligand with an amine moiety is formed as a kinetic product, which isomerizes via net oxidative addition of the amine N−H to phosphorous to yield a benzoxazaphosphole-containing thermodynamic product. Both isomers undergo productive metallation with NiBr2 (dimethoxyethane) to produce the same complex, (P2 ONO)NiBr. Treatment with triethylborohydride furnished the terminal hydride complex (P2 ONO)NiH. The bromide and hydride complexes enabled comparisons of the steric and electronic properties of the P2 ONO − ligand with other amide-based pincers.