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Rhodium and Iridium Complexes with α-Diketimine Ligands: Oxidative Addition of H2 and O2

✍ Scribed by Anna Penner; Thomas Braun

Publisher
John Wiley and Sons
Year
2011
Tongue
English
Weight
445 KB
Volume
2011
Category
Article
ISSN
1434-1948

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✦ Synopsis

Abstract

The treatment of [M(μ‐Cl)(coe)~2~]~2~ (M = Rh, Ir; coe = cyclooctene) with the α‐diketimines ArN=C(Me)C(Me)=NAr (Ar = Ph, Xy; Xy = 2,6‐Me~2~C~6~H~3~) in thf, followed by the addition of CN__t__Bu, gave the α‐diketimine complexes [M(Cl){ArN=C(Me)C(Me)=NAr} (CN__t__Bu)] (1: M = Rh, Ar = Ph; 2: M = Rh, Ar = Xy; 3: M = Ir, Ar = Xy). The reaction of 3 with dihydrogen resulted in the formation of the iridium dihydrido complex [Ir(Cl)(H)~2~{XyN=C(Me)C(Me)=NXy}(CN__t__Bu)] (4). The complexes 2 and 3 reacted with O~2~ or ^18^O~2~ to yield the peroxido complexes [M(Cl)(O~2~){XyN=C(Me)C(Me)=NXy}(CN__t__Bu)] (5a: M = Rh; 6a: M = Ir) and [M(Cl)(^18^O~2~){XyN=C(Me)C(Me)=NXy}(CN__t__Bu)] (5b: M = Rh; 6b: M = Ir), respectively. All of the complexes were characterized by NMR and IR spectroscopy. In addition, complexes 3 and 5a were characterized by X‐ray crystallography.

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## Abstract Heating [Rh(dtbpy)(κ~2~‐__C,C′__‐CH~2~CMe~2~C~6~H~4~)(CH~2~CMe~2~Ph)] (1; dtbpy = 4,4′‐di‐__tert__‐butyl‐2,2′‐bipyridyl) in __p__‐xylene at 110 °C resulted in the formation of the 2‐__tert__‐butylphenyl complex [Rh(dtbpy)(κ~2~‐__C,C′__‐CH~2~CMe~2~C~6~H~4~)(C~6~H~4~__t__Bu‐2)] (3). Treat