%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)HIrBH3(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)HIrBH3(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 }