Ambiphilic Reactivity of a Ruthenaphosphaalkenyl: Synthesis of <i>P</i>‑Pyrazolylphosphaalkene Complexes of Ruthenium(0)
dataset
posted on 2013-05-13, 00:00 authored by Nicola Trathen, Victoria K. Greenacre, Ian R. Crossley, S. Mark RoeThe novel ruthenaphosphaalkenyl complex
[Ru{PCH(SiMe<sub>3</sub>)}Cl(CO)(PPh<sub>3</sub>)<sub>2</sub>], prepared from [RuHCl(CO)(PPh<sub>3</sub>)<sub>3</sub>] and Me<sub>3</sub>SiCP, exhibits ambiphilic
behavior, reacting at phosphorus with both nucleophiles and electrophiles.
Its reaction with Li(pz′) or K[HB(pz′)<sub>3</sub>]
(pz′ = pz, pz*) affords [Ru{η<sup>1</sup>-<i>N</i>:η<sup>2</sup><i>-P</i>,<i>C-</i>P(pz′)CH(SiMe<sub>3</sub>)}(CO)(PPh<sub>3</sub>)<sub>2</sub>], a rare example of a
ruthenium(0) η<sup>2</sup>-phosphaalkene complex and the first
example of a <i>P</i>-pyrazolylphosphaalkene. Conversely,
reaction with the electrophilic PhHgCl leads to metalation at phosphorus,
affording [Ru{η<sup>1</sup>-P(HgPh)CH(SiMe<sub>3</sub>)}Cl<sub>2</sub>(CO)(PPh<sub>3</sub>)<sub>2</sub>].
