10.1021/om5012177.s002
Victoria
K. Greenacre
Victoria
K.
Greenacre
Nicola Trathen
Nicola
Trathen
Ian R. Crossley
Ian R.
Crossley
Ruthenaphosphaalkenyls: Synthesis, Structures, and
Their Conversion to η<sup>2</sup>‑Phosphaalkene Complexes
American Chemical Society
2015
Ru
novel compounds
ruthena
pz
nucleophilic character
phospha
DFT studies
2015-06-08 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Ruthenaphosphaalkenyls_Synthesis_Structures_and_Their_Conversion_to_sup_2_sup_Phosphaalkene_Complexes/2160532
The
ruthenaphosphaalkenyls [Ru{PCH(SiMe<sub>2</sub>R)}Cl(CO)(PPh<sub>3</sub>)<sub>2</sub>] (R = Me, Ph,
Tol) have been prepared in good yield by the facile hydroruthenation
of the respective phosphaalkynes, RMe<sub>2</sub>SiCP,
with [RuHCl(CO)(PPh<sub>3</sub>)<sub>3</sub>]; all three compounds
have been structurally characterized in the solid state. Complemented
by DFT studies of these, and the precedent [Ru{PCH(<sup><i>t</i></sup>Bu)}Cl(CO)(PPh<sub>3</sub>)<sub>2</sub>], the
phosphaalkenyl moieties have been established unequivocally
to behave as one-electron donors to the coordinately unsaturated,
15-electron “RuCl(CO)(PPh<sub>3</sub>)<sub>2</sub>”
fragment, corroborating an earlier demonstration of nucleophilic character
at phosphorus within the <i>tert-</i>butyl system. Notwithstanding,
the ruthenaphosphaalkenyls are shown to react with the
nucelophiles Lipz′ (pz′ = pz, pz*, pz<sup>H,CF<sub>3</sub></sup>, pz<sup>Me,CF<sub>3</sub></sup>) to afford the η<sup>1</sup>,η<sup>2</sup>-chelated pyrazolylphosphaalkene
complexes [Ru{η<sup>1</sup>-<i>N</i>:η<sup>2</sup><i>-P,C-</i>P(pz′)CH(R)}(CO)(PPh<sub>3</sub>)<sub>2</sub>], which feature a three-membered metallacyclic
(Ru–C–P) core. The nature of these novel compounds is
discussed, alongside preliminary insight into the process by which
they are formed.