Anionic linear chain iridium carbonyl halides

Ginsberg, A. P.; Koepke, J. W.; Hauser, J. J.; West, K. W.; Salvo, F. J. Di; Sprinkle, C. R.; Cohen, Richard L.

doi:10.1021/ic50157a005

Cited by 37 publications

(14 citation statements)

References 18 publications

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“…IR measurements can give information about the relative disposition of the chloro ligands in organometallic [Ir]Cl 2 fragments. Thus, for a cis disposition two IR-active ν(IrCl) frequencies are expected in the region 400−200 cm -1 , while a trans disposition would display only one characteristic band . IR spectra of 14A and the 3:4:2 mixture of 14A : 14B : 14C were recorded in the range 700−200 cm -1 (solid state, CsI pellets).…”

Section: Resultsmentioning

confidence: 99%

Asymmetric Iridium(I)-Catalyzed Allylic Alkylation of Monosubstituted Allylic Substrates with Phosphinooxazolines as Ligands. Isolation, Characterization, and Reactivity of Chiral (Allyl)iridium(III) Complexes

et al. 2004

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Ir I -catalyzed allylic alkylations of linear aryl-substituted allylic acetates proceed with enantiomeric excess of up to 95% ee using bidentate phosphinooxazolines as chiral ligands. The chiral (π-allyl)Ir III complexes 14 and 15 have been characterized by X-ray crystal structure analysis and spectroscopic data. The stoichiometric reaction between sodium dimethyl malonate and complex 14 proceeded with nucleophilic addition at the central allylic carbon as well as ligand exchange at Ir to give the iridacyclobutane complex 16, which was fully characterized. Complex 16 was transformed into (π-allyl)Ir III complexes by treatment with Lewis acid or iodine.

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Section: Resultsmentioning

confidence: 99%

Asymmetric Iridium(I)-Catalyzed Allylic Alkylation of Monosubstituted Allylic Substrates with Phosphinooxazolines as Ligands. Isolation, Characterization, and Reactivity of Chiral (Allyl)iridium(III) Complexes

et al. 2004

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“…Older compounds in this series include A 0.60 Ir(CO) 2 X 2 , with A = K, Cs, TTF (TTF = tetrathiafulvalene). [ 15 ] Newer ones arise from electrochemically oxidized [Ir(CO) 2 X 2 ] -, X = Cl, Br, I. [16,17] And there is the beautiful series of partially supported oxidized Ir chains from the Oro and Ciriano groups, [18,19,20,21,22] one example of which is shown in Fig.…”

Section: Introductionmentioning

confidence: 99%

Revisiting Ir(CO)3Cl

2016

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We return to an old puzzlethe short metal-metal separation and electrical conductivity of the apparently unoxidized one-dimensionally stacked structure of a d 8 Ir(I) complex, Ir(CO) 3 Cl. One would expect neither a short Ir-Ir distance of 2.84 Å, nor metallicity in an unoxidized stacked square-planar d 8 array. We build up dimer, trimer, one-dimensional polymer and model 3-dimensional structures, in both molecular and extended structure plane wave calculations. The short Ir-Ir separation in the polymer, with a substantial contribution of 6p z -5d z2 bonding to it, is obtained without any oxidation. There is computational evidence for an important level crossing in the polymer. The metallicity remains unexplained, but likely arises from partial oxidation. And that remains an outstanding experimental issue. ] G. A. Landrum, YAeHMOP: Yet Another extended Hückel Molecular Orbital Package, Version 3.0; http://sourceforge.net/projects/yaehmop/. *Graphical Abstract -Pictogram (for review)One would expect neither a short Ir-Ir distance of 2.84 Å, nor metallicity in an unoxidized stacked square-planar d 8 array, as one sees in the structure of Ir(CO) 3 Cl. In calculations, a short Ir-Ir separation is obtained and explained, without any oxidation. The metallicity remains a puzzle. *Graphical Abstract -Synopsis (for review)

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“…Namely, the known partial oxidation process involving the metal centres in the Ru 0 -Ru 0 chain [6,14], the short Ru-Ru bond length and the proposed structure [16] makes the material similar to well conducting, partially oxidised chains formed by stacking of e.g. square-planar Pt [17] or Ir [18] d 8 complexes. We have also recently found that the film conductance increases following partial oxidation [19].…”

Section: Introductionmentioning

confidence: 99%