10.1021/om970981x.s001
Cristina Tejel
Cristina
Tejel
Miguel A. Ciriano
Miguel A.
Ciriano
José A. López
José A.
López
Fernando J. Lahoz
Fernando J.
Lahoz
Luis A. Oro
Luis A.
Oro
Unusual Tautomers in Dinuclear Metal Chemistry and
Their Role in Oxidative-Addition Reactions of
Chlorocarbons
American Chemical Society
1998
Dinuclear Metal Chemistry
PhCH 2 Cl
tautomeric equilibrium
MeCO 2 CH 2 Cl
CNBu
Unusual Tautomers
Ir
MeCO 2 CH 2
1998-03-20 00:00:00
Journal contribution
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.