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Updated: Aug 15, 2026

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)
Published on: November 22, 2016
Oxygen atom transfer reactivity from a dioxo-Mo(VI) complex to tertiary phosphines: synthesis, characterization, and
Victor N Nemykin1, Partha Basu
1Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282, USA.
Abstract:
The oxygen atom transfer (OAT) reactivity of TpMoO2Cl with PMe3, PEt3, and PPhMe2 (where Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate) has been investigated. The OAT reactions proceed through a diamagnetic Mo(IV) phosphoryl intermediate complex of general formula TpMoOCl(OPR3) (OPR3 = OPMe3, OPEt3, OPPhMe2), which have been isolated and characterized by 1H and 31P NMR, UV-visible, and infrared spectroscopies and electrospray ionization mass spectrometry. Solid-state crystal structures of TpMoOCl(OPMe3) and TpMoOCl(OPPhMe2) are also reported, the oxygen-to-phosphorus distances agree with a double-bond formulation and a single bond between the metal and the phosphoryl oxygen atom. The stability of the phosphoryl intermediate complexes depends on the steric properties of the coordinated phosphine-oxides. These intermediate complexes have been converted to solvent-coordinated species, TpMoOCl(solv) (solv = acetonitrile or dmf), and the coordinated solvents exchange with the bulk solvent.
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