Unusual Tautomers in Dinuclear Metal Chemistry and
Their Role in Oxidative-Addition Reactions of
Chlorocarbons
Cristina Tejel
Miguel A. Ciriano
José A. López
Fernando J. Lahoz
Luis A. Oro
10.1021/om970981x.s001
https://acs.figshare.com/articles/journal_contribution/Unusual_Tautomers_in_Dinuclear_Metal_Chemistry_and_Their_Role_in_Oxidative-Addition_Reactions_of_Chlorocarbons/3781458
The complex
[{Ir(μ-Pz)(CNBu<sup>t</sup>)<sub>2</sub>}<sub>2</sub>(Cl)(CH<sub>2</sub>Ph)] (<b>2</b>), obtained by reaction of
[{Ir(μ-Pz)(CNBu<sup>t</sup>)<sub>2</sub>}<sub>2</sub>]
(<b>1</b>)
with PhCH<sub>2</sub>Cl, presents a very unusual
tautomeric
equilibrium between the metal−metal-bonded and the
mixed-valence complexes
[(CNBu<sup>t</sup>)<sub>2</sub>(Cl)Ir(μ-Pz)<sub>2</sub>Ir(CH<sub>2</sub>Ph)(CNBu<sup>t</sup>)<sub>2</sub>] and
[(CNBu<sup>t</sup>)<sub>2</sub>Ir(μ-Pz)<sub>2</sub>Ir(Cl)(CH<sub>2</sub>Ph)(CNBu<sup>t</sup>)<sub>2</sub>], respectively. This equilibrium
allows the
unprecedented oxidative-addition reaction of chloroalkanes such as PhCH<sub>2</sub>Cl and
MeCO<sub>2</sub>CH<sub>2</sub>Cl to the
diiridium(II) complex <b>2</b>, resulting in the
diiridium(III)
complex
[{Ir(μ-Pz)(CH<sub>2</sub>Ph)(CNBu<sup>t</sup>)<sub>2</sub>}<sub>2</sub>(μ-Cl)]Cl
and the
mixed-dialkyl complex
[(CNBu<sup>t</sup>)<sub>2</sub>(MeCO<sub>2</sub>CH<sub>2</sub>)Ir(μ-Pz)<sub>2</sub>(μ-Cl)Ir(CH<sub>2</sub>Ph)(CNBu<sup>t</sup>)<sub>2</sub>]Cl,
respectively.
1998-03-20 00:00:00
Dinuclear Metal Chemistry
PhCH 2 Cl
tautomeric equilibrium
MeCO 2 CH 2 Cl
CNBu
Unusual Tautomers
Ir
MeCO 2 CH 2