Cationic Five-Coordinate Bis(butadiene)iridium(I) Complexes from the Highly Labilecis-[Ir(η2-C8H14)2(acetone)2]+ Cation as the Precursor

Bosch, Marco; Ilg, Kerstin; Werner, Helmut

doi:10.1002/1099-0682(200112)2001:12<3181::aid-ejic3181>3.0.co;2-y

Cited by 5 publications

(2 citation statements)

References 25 publications

(16 reference statements)

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“…We describe here the synthesis of solvent-stabilized, cationic Ir(I)−COE complexes (COE = cyclooctene), whose isolation as analytically pure compounds failed in the past . These Ir(I) complexes undergo selective substitution of cyclooctene by alkylphosphines, and intramolecular C−H activation (cyclometalation) of bulky alkylphosphines (i.e.…”

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confidence: 99%

Reactivity of [Ir(COE)₂(solvent)₂]PF₆ Complexes toward Alkylphosphines: Room-Temperature C−H Activation (Cyclometalation) and Isolation of a 14-Electron Alkyl−Iridium(III) Complex

2003

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Isolated, cationic bis(cyclooctene)−Ir(I) complexes stabilized by acetonitrile or acetone solvent molecules were obtained and reacted with simple alkylphosphines, leading to selective displacement of the cyclooctene ligand. With the bulky tBu3P, facile intramolecular C−H activation is observed, giving cyclometalated, solvent-stabilized bis(phosphine)−Ir(III) species and leading to the isolation of the first 14-electron alkyl−Ir(III) complex.

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confidence: 99%

Reactivity of [Ir(COE)₂(solvent)₂]PF₆ Complexes toward Alkylphosphines: Room-Temperature C−H Activation (Cyclometalation) and Isolation of a 14-Electron Alkyl−Iridium(III) Complex

2003

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“…We were interested in preparing dicationic Ir complexes, bearing our PNP ligand and stabilized by a weakly coordinated solvent molecule. For this purpose, we utilized a cationic precursor [Ir(COE) 2 {acetone} 2 ]PF 6 prepared from [IrCl(COE) 2 ] 2 . Reaction of ligand 2b with an equivalent amount of [Ir(COE) 2 {acetone} 2 ]PF 6 in acetonitrile smoothly led to the formation of a purple solution of complex 5 .…”

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confidence: 75%

Synthesis and Characteristics of Iridium Complexes Bearing N-Heterocyclic Nitrenium Cationic Ligands

et al. 2019

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N-Heterocyclic nitrenium cations are isostructural and isoelectronic analogues of the ubiquitous N-heterocyclic carbene. We present the first examples of coordination of nitrenium ions to the Ir(I) and Ir(III) metal centers. This work includes rare complexes with cation–cation interactions between a positively charged ligand and an iridium ion. These species represent the first example of iridium complexes bearing any cationic ligand of group 15 elements analogous to the Arduengo carbene. These nitrenium-based monocationic and even dicationic Ir(I) complexes can smoothly oxidatively activate H2 at room temperature and ambient pressure. Utilizing our system, we were able to observe an Ir–dihydrogen σ-complex, which undergoes oxidative addition to yield a well-defined Ir(III) dihydride. Comparative studies of the analogous Rh(I)–nitrenium species, which exhibit reversible dihydrogen activation, are presented. New Ir complexes were fully characterized by multinuclear nuclear magnetic resonance (including 15N labeling) and X-ray crystallography.

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Secondary Interactions or Ligand Scrambling? Subtle Steric Effects Govern the Iridium(I) Coordination Chemistry of Phosphoramidite Ligands

Osswald

Rüegger

Mezzetti

2010

Chemistry A European J

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The like and unlike isomers of phosphoramidite (P*) ligands are found to react differently with iridium(I), which is a key to explaining the apparently inconsistent results obtained by us and other research groups in a variety of catalytic reactions. Thus, the unlike diastereoisomer (aR,S,S)-[IrCl(cod)(1 a)] (2 a; cod=1,5-cyclooctadiene, 1 a=(aR,S,S)-(1,1'-binaphthalene)-2,2'-diyl bis(1-phenylethyl)phosphoramidite) forms, upon chloride abstraction, the monosubstituted complex (aR,S,S)-[Ir(cod)(1,2-eta-1 a,kappaP)](+) (3 a), which contains a chelating P* ligand that features an eta(2) interaction between a dangling phenyl group and iridium. Under analogous conditions, the like analogue (aR,R,R)-1 a' gives the disubstituted species (aR,R,R)-[Ir(cod)(1 a',kappaP)(2)](+) (4 a') with monodentate P* ligands. The structure of 3 a was assessed by a combination of X-ray and NMR spectroscopic studies, which indicate that it is the configuration of the binaphthol moiety (and not that of the dangling benzyl N groups) that determines the configuration of the complex. The effect of the relative configuration of the P* ligand on its iridium(I) coordination chemistry is discussed in the context of our preliminary catalytic results and of apparently random results obtained by other groups in the iridium(I)-catalyzed asymmetric allylic alkylation of allylic acetates and in rhodium(I)-catalyzed asymmetric cycloaddition reactions. Further studies with the unlike ligand (aS,R,R)-(1,1'-binaphthalene)-2,2'-diyl bis{[1-(1-naphthalene-1-yl)ethyl]phosphoramidite} (1 b) showed a yet different coordination mode, that is, the eta(4)-arene-metal interaction in (aS,R,R)-[Ir(cod)(1,2,3,4-eta-1 b,kappaP)](+) (3 b).

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Cationic Five-Coordinate Bis(butadiene)iridium(I) Complexes from the Highly Labilecis-[Ir(η2-C8H14)2(acetone)2]+ Cation as the Precursor

Cited by 5 publications

References 25 publications

Reactivity of [Ir(COE)₂(solvent)₂]PF₆ Complexes toward Alkylphosphines: Room-Temperature C−H Activation (Cyclometalation) and Isolation of a 14-Electron Alkyl−Iridium(III) Complex

Reactivity of [Ir(COE)₂(solvent)₂]PF₆ Complexes toward Alkylphosphines: Room-Temperature C−H Activation (Cyclometalation) and Isolation of a 14-Electron Alkyl−Iridium(III) Complex

Synthesis and Characteristics of Iridium Complexes Bearing N-Heterocyclic Nitrenium Cationic Ligands

Secondary Interactions or Ligand Scrambling? Subtle Steric Effects Govern the Iridium(I) Coordination Chemistry of Phosphoramidite Ligands

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Cationic Five-Coordinate Bis(butadiene)iridium(I) Complexes from the Highly Labilecis-[Ir(η2-C8H14)2(acetone)2]+ Cation as the Precursor

Cited by 5 publications

References 25 publications

Reactivity of [Ir(COE)2(solvent)2]PF6 Complexes toward Alkylphosphines: Room-Temperature C−H Activation (Cyclometalation) and Isolation of a 14-Electron Alkyl−Iridium(III) Complex

Reactivity of [Ir(COE)2(solvent)2]PF6 Complexes toward Alkylphosphines: Room-Temperature C−H Activation (Cyclometalation) and Isolation of a 14-Electron Alkyl−Iridium(III) Complex

Synthesis and Characteristics of Iridium Complexes Bearing N-Heterocyclic Nitrenium Cationic Ligands

Secondary Interactions or Ligand Scrambling? Subtle Steric Effects Govern the Iridium(I) Coordination Chemistry of Phosphoramidite Ligands

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Reactivity of [Ir(COE)₂(solvent)₂]PF₆ Complexes toward Alkylphosphines: Room-Temperature C−H Activation (Cyclometalation) and Isolation of a 14-Electron Alkyl−Iridium(III) Complex

Reactivity of [Ir(COE)₂(solvent)₂]PF₆ Complexes toward Alkylphosphines: Room-Temperature C−H Activation (Cyclometalation) and Isolation of a 14-Electron Alkyl−Iridium(III) Complex