10.1021/acs.organomet.7b00688.s001
María
F. Espada
María
F.
Espada
Ana C. Esqueda
Ana C.
Esqueda
Jesús Campos
Jesús
Campos
Miguel Rubio
Miguel
Rubio
Joaquín López-Serrano
Joaquín
López-Serrano
Eleuterio Álvarez
Eleuterio
Álvarez
Celia Maya
Celia
Maya
Ernesto Carmona
Ernesto
Carmona
Cationic (η<sup>5</sup>‑C<sub>5</sub>Me<sub>4</sub>R)Rh<sup>III</sup> Complexes with Metalated Aryl Phosphines
Featuring η<sup>4</sup>‑Phosphorus plus Pseudo-Allylic Coordination
American Chemical Society
2017
PR
complexes 3
metalated phosphine exhibits η 4 coordination
CO
DFT
NMR
C 5
III
Lewis acid behavior
phosphine Ar groups feature methyl substituents
2017-12-20 18:03:43
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Cationic_sup_5_sup_C_sub_5_sub_Me_sub_4_sub_R_Rh_sup_III_sup_Complexes_with_Metalated_Aryl_Phosphines_Featuring_sup_4_sup_Phosphorus_plus_Pseudo-Allylic_Coordination/5723230
In this contribution we study experimentally
and computationally
some electrophilic cationic (η<sup>5</sup>-C<sub>5</sub>Me<sub>4</sub>R)Rh<sup>III</sup> complexes containing a cyclometalated bis(aryl)
phosphine, PR′Ar<sub>2</sub>. The phosphine Ar groups feature
methyl substituents at the 2- and 6-positions of the aromatic rings,
allowing the formation of the complexes [(η<sup>5</sup>-C<sub>5</sub>Me<sub>4</sub>R)Rh(C<sup>∧</sup>P)]<sup>+</sup> (<b>3</b><sup><b>+</b></sup>), where the metalated phosphine
exhibits η<sup>4</sup> coordination to rhodium through phosphorus
and the carbon atoms of the adjoining pseudo-allylic functionality.
The solution and solid-state structures of complexes <b>3</b><sup><b>+</b></sup> have been studied by NMR and X-ray methods
and their electronic properties investigated with the aid of DFT calculations.
The Lewis acid behavior of complexes <b>3</b><sup><b>+</b></sup> has also been addressed, concentrating on reactivity toward
CO, H<sub>2</sub> ,and hydrosilanes. Some catalytic Si–H/Si–D
exchange and hydrosilylation reactions are also reported.