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Updated: Aug 14, 2026

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)
Published on: November 22, 2016
Transformation of organic molecules on the low-valent [M(Ph(2)PCH(2)CH(2)PPh(2))(2)] moiety derived from
1Institute of Industrial Science, the University of Tokyo, Komaba, Tokyo 153-8505, Japan.
Abstract:
A zero-valent [M(Ph(2)PCH(2)CH(2)PPh(2))(2)] moiety (M = Mo, W) generated in situ by dissociation of the N(2) ligands in trans-[M(N(2))(2)(Ph(2)PCH(2)CH(2)PPh(2))(2)] can activate pi-accepting organic molecules including isocyanides and nitriles, which undergo the electrophilic attack caused by a strong pi-donation from a zero-valent metal center. Cleavage of a variety of C-X bonds (X = H, C, N, O, P, halogen) also occurs at their electron-rich sites through oxidative addition to form reactive intermediates, which subsequently degradate to yield smaller molecules either bound to or dissociated from the metal center. The mechanism is substantiated unambiguously by isolation of numerous intermediate stages.
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