Article,

Qualitatively Different Reactivities of Hydride Reagents toward [(a-diimine)(h5-C5Me5)ClIr]+ Cations: Substitution, Electron Transfer (Reduction), or Stepwise Hydrogenation

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Organometallics, 21 (4): 765--769 (2002)
DOI: 10.1021/om010529k

Abstract

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)]

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