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{PCH­(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>SiCP, 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{PCH­(<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.