Qualitatively Different Reactivities of Hydride Reagents toward [(a-diimine)(h5-C5Me5)ClIr]+ Cations: Substitution, Electron Transfer (Reduction), or Stepwise Hydrogenation
Whereas complex cations [(a-diimine)(h5-C5Me5)ClIr]+ with 2,2'-bipyridine and related arom. ligands show only the expected Cl/H exchange on reaction with borohydrides, the systems [(RN:CHCH:NR)(h5-C5Me5)ClIr]+ undergo redn. to the enediamido(2-)-Ir(III) species [(RNCH:CHNR)(h5-C5Me5)Ir], even in protic media, if R is an axially shielding 2,6-dialkylphenyl group. In protic media the complex ion with R = cyclohexyl undergoes Cl/H exchange and stepwise hydrogenation of the a-diimine ligand via [(RHNCH2CH:NR)(h5-C5Me5)HIr](PF6) to the structurally characterized compd. [(RHNCH2CH2NHR)(h5-C5Me5)HIr][BH3(CN)]. Results of cyclic voltammetry studies are also presented. The crystal and mol. structures of [(RN:CHCH:NR)(h5-C5Me5)ClIr](PF6) (R = o-tolyl) and [(RHNCH2CH2NHR)(h5-C5Me5)HIr][BH3(CN)] (R = cyclohexyl) were detd. by x-ray crystallog. [on SciFinder(R)]
%0 Journal Article
%1 Greulich.2002
%A Greulich, Stefan
%A Klein, Axel
%A Knoedler, Axel
%A Kaim, Wolfgang.
%D 2002
%J Organometallics
%K aminoethylimine chloro complex complex;cyclic complex;enediamido crystal cyclopentadienyl diamine diimine hydrogenation iridium prepn prepn;hydrido prepn;iridium redn structure substitution;mol voltammetry
%N 4
%P 765--769
%R 10.1021/om010529k
%T Qualitatively Different Reactivities of Hydride Reagents toward [(a-diimine)(h5-C5Me5)ClIr]+ Cations: Substitution, Electron Transfer (Reduction), or Stepwise Hydrogenation
%V 21
%X Whereas complex cations [(a-diimine)(h5-C5Me5)ClIr]+ with 2,2'-bipyridine and related arom. ligands show only the expected Cl/H exchange on reaction with borohydrides, the systems [(RN:CHCH:NR)(h5-C5Me5)ClIr]+ undergo redn. to the enediamido(2-)-Ir(III) species [(RNCH:CHNR)(h5-C5Me5)Ir], even in protic media, if R is an axially shielding 2,6-dialkylphenyl group. In protic media the complex ion with R = cyclohexyl undergoes Cl/H exchange and stepwise hydrogenation of the a-diimine ligand via [(RHNCH2CH:NR)(h5-C5Me5)HIr](PF6) to the structurally characterized compd. [(RHNCH2CH2NHR)(h5-C5Me5)HIr][BH3(CN)]. Results of cyclic voltammetry studies are also presented. The crystal and mol. structures of [(RN:CHCH:NR)(h5-C5Me5)ClIr](PF6) (R = o-tolyl) and [(RHNCH2CH2NHR)(h5-C5Me5)HIr][BH3(CN)] (R = cyclohexyl) were detd. by x-ray crystallog. [on SciFinder(R)]
@article{Greulich.2002,
abstract = {Whereas complex cations [(\textgreek{a}-diimine)(\textgreek{h}5-C5Me5)ClIr]+ with 2,2'-bipyridine and related arom. ligands show only the expected Cl/H exchange on reaction with borohydrides, the systems [(RN:CHCH:NR)(\textgreek{h}5-C5Me5)ClIr]+ undergo redn. to the enediamido(2-)-Ir(III) species [(RNCH:CHNR)(\textgreek{h}5-C5Me5)Ir], even in protic media, if R is an axially shielding 2,6-dialkylphenyl group. In protic media the complex ion with R = cyclohexyl undergoes Cl/H exchange and stepwise hydrogenation of the \textgreek{a}-diimine ligand via [(RHNCH2CH:NR)(\textgreek{h}5-C5Me5)HIr](PF6) to the structurally characterized compd. [(RHNCH2CH2NHR)(\textgreek{h}5-C5Me5)HIr][BH3(CN)]. Results of cyclic voltammetry studies are also presented. The crystal and mol. structures of [(RN:CHCH:NR)(\textgreek{h}5-C5Me5)ClIr](PF6) (R = o-tolyl) and [(RHNCH2CH2NHR)(\textgreek{h}5-C5Me5)HIr][BH3(CN)] (R = cyclohexyl) were detd. by x-ray crystallog. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Greulich, Stefan and Klein, Axel and Knoedler, Axel and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2bd8e90f1794abdfd7dd29267c35768f7/huebleriac},
doi = {10.1021/om010529k},
interhash = {b77f7d5e173dddae1db740405ad0d155},
intrahash = {bd8e90f1794abdfd7dd29267c35768f7},
issn = {0276-7333},
journal = {Organometallics},
keywords = {aminoethylimine chloro complex complex;cyclic complex;enediamido crystal cyclopentadienyl diamine diimine hydrogenation iridium prepn prepn;hydrido prepn;iridium redn structure substitution;mol voltammetry},
number = 4,
pages = {765--769},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Qualitatively Different Reactivities of Hydride Reagents toward [(\textgreek{a}-diimine)(\textgreek{h}5-C5Me5)ClIr]+ Cations: Substitution, Electron Transfer (Reduction), or Stepwise Hydrogenation},
volume = 21,
year = 2002
}