Nucleophilic Substitution of η<sup>5</sup>-Pyrrolyl Ligands in
Ruthenium(II) Complexes
M. Rakowski DuBois
K. G. Parker
C. Ohman
B. C. Noll
10.1021/om9700268.s001
https://acs.figshare.com/articles/journal_contribution/Nucleophilic_Substitution_of_sup_5_sup_-Pyrrolyl_Ligands_in_Ruthenium_II_Complexes/3779430
The reaction of
RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> with
pyrrolyllithium results in the formation of the pyrrolyl
complex
(NC<sub>4</sub>H<sub>4</sub>)RuCl(PPh<sub>3</sub>)<sub>2</sub>,
<b>1</b>, which has been characterized by an X-ray diffraction
study.
The structure confirms the η<sup>5</sup>-bonding mode for the
pyrrolyl ligand. Ligand substitution
reactions with <b>1</b> have led to the facile synthesis of related
η<sup>5</sup>-pyrrolyl ruthenium complexes
with other suppporting ligands. Reactions of the PEt<sub>3</sub>
derivatives
(NC<sub>4</sub>H<sub>4</sub>)RuX(PEt<sub>3</sub>)<sub>2</sub>,
X =
Cl and I, with aryl- and alkyllithium reagents resulted in nucleophilic
substitution of the
pyrrolyl ligand accompanied by hydrogen transfer to the metal ion,
forming (2-RNC<sub>4</sub>H<sub>3</sub>)RuH(PEt<sub>3</sub>)<sub>2</sub>. The hydride products could
be converted to the corresponding chloride
derivatives in chlorinated solvents, and the complex
(2-PhNC<sub>4</sub>H<sub>3</sub>)RuCl(PEt<sub>3</sub>)<sub>2</sub>
has been
structurally characterized. A second nucleophilic substitution
reaction on the coordinated
pyrrolyl ligand has been characterized in some cases, and protonation
of the substituted
pyrrole complex led to isolation of the free substituted pyrrole with
recycling of the ruthenium
complex. The nucleophilic substitutions are sensitive to the
electronic features of the
supporting ligands in the complex and to the strength of the
nucleophiles.
1997-05-27 00:00:00
nucleophilic substitution reaction
pyrrolyl ruthenium complexes
RuCl
RNC
PEt 3 derivatives
pyrrole
Ligand substitution reactions
pyrrolyl ligand
η 5
NC 4 H 4