Fluorination of tetrairidium dodecacarbonyl

Brewer, Stuart A.; Holloway, John H.; Hope, Eric G.; Watson, Paul G.

doi:10.1039/c39920001577

Cited by 20 publications

(21 citation statements)

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“…The subsequent molecular structure determination and vibrational spectra of the crystals indicate conclusively that in the crystalline solid only the meridional isomer is present and is apparently less soluble in HSO 3 F than the fac -isomer. The opposite observation has recently been reported for Ir(CO) 3 F 3 in a solution of anhydrous HF, where according to solution NMR at −78 °C ( 19 F and 13 C) and the IR spectrum of the isolated solid, the facial isomer is predominant. A fac- isomer is also suggested for Ir(CO) 3 I 3 …”

Section: Introductioncontrasting

confidence: 54%

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)₃(SO₃F)₃

et al. 1996

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Addition of carbon monoxide (0.5-2 atm) to iridium(III) fluorosulfate, Ir(SO(3)F)(3), dissolved in HSO(3)F over 4 days and at 60 degrees C, results in the quantitative formation of tris(carbonyl)iridium(III) fluorosulfate Ir(CO)(3)(SO(3)F)(3). Slow evaporation of the solvent produces single crystals of mer-Ir(CO)(3)(SO(3)F)(3). Crystal structure data for mer-Ir(CO)(3)(SO(3)F)(3): monoclinic, space group P2(1)/c, Z = 4, a = 8.476(1) Å, b = 12.868(2) Å, c = 12.588 (1) Å, beta = 108.24(1) degrees, V = 1304.0 Å(3), T = 200 K, R(F)() = 0.022 for 2090 data (I(o) >/= 2.5sigma(I(o))) and 200 variables. Vibrational spectra of the crystalline solid are consistent with a mer-isomer with CO stretching modes at 2249 (A(1)), 2208 (B(1)), and 2198 (A(1)) cm(-)(1) in the IR spectrum. In solution of HSO(3)F, additional CO stretching bands attributed to the fac-isomer are found in the FT-Raman and IR spectra at 2233 (A(1)) and 2157 cm(-)(1) (E). Additional evidence for a mixture of fac- and mer-isomers comes from (19)F NMR spectra. The vibrational spectra suggest strongly reduced iridium to CO pi-back-bonding. The crystal structure reveals significant intra- and intermolecular contacts between the electropositive C atom of the CO groups and O or F atoms of the fluorosulfate groups. Hence mer-tris(carbonyl)iridium(III) fluorosulfate becomes the first thermally stable, structurally characterized, and predominantly sigma-bonded carbonyl derivative of a metal in the +3 oxidation state.

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Section: Introductioncontrasting

confidence: 54%

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)₃(SO₃F)₃

et al. 1996

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“…The complex is readily characterised in solution by NMR spectroscopy: The 19 F NMR spectrum consists of two mutually-coupled resonances, a doublet of triplets at d -451.2 and a lower field triplet of triplets at d -280.9. The high field resonance is typical of an F-trans-F interaction across Ir(III) 13, 21 and is, therefore, assigned to the two trans fluorines (F A ; Scheme 1). The remaining resonance is typical of an F-trans-CO moiety across Ir(III) (F B ).…”

Section: Resultsmentioning

confidence: 99%

“…For the all-trans isomers, the 19 F NMR resonances occur at substantially lower frequencies and the 2 J PF coupling constants are larger than those for the cis-difluoride isomers, as expected for the F-trans-F and F-cis-F arrangements. 13,[21][22][23][24] In the oxidations of the a-diimine complexes, the corresponding iridium(III) difluoride cations are formed as the single F-trans-F isomers, trans-,cis- 2), for which the shifts in d F to low frequency, in comparison to those for the related COD-complexes, mirror those for the related pairs of monodentate phosphine complexes.…”

Section: Methodsmentioning

confidence: 99%

“…29 Syntheses. fac-Iridiumtricarbonyltrifluoride (1) 21 . Tetrairidiumdodecacarbonyl (1 g, 0.9 mmol) was dissolved in aHF (2 cm 3 ) in a 10 mm O.D., 1.5 mm wall thickness pre-passivated FEP vessel fitted with a PTFE valve.…”

Section: Experimental General Remarksmentioning

confidence: 99%

“…Found: C, 52. The other iridium difluorocations (11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22) were prepared similarly in quantitative yields.…”

Section: Experimental General Remarksmentioning

confidence: 99%

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Synthesis and characterisation of some iridium-carbonyl-fluoride complexes. Crystal structures of [IrF(CO){P(C6H4-2-CH3)3}2] and [IrF2(COD)py2][BF4]

2010

Self Cite

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Two routes to iridium(III) fluorocomplexes are described. The direct reaction of tetrairidium dodecacarbonyl with elemental fluorine in aHF offers a clean, convenient, large scale route to [IrF(3)(CO)(3)]; addition of phosphines to [IrF(3)(CO)(3)] in THF affords mer-[IrF(3)(CO)L(2)] or [IrF(CO)L(2)]. Alternatively, cationic [IrF(2)(COD)L(2)](+) and [IrF(2)(CO)(2)L(2)](+) (L = phosphine, pyridine; L(2) = alpha-diimine) are accessible via the oxidation of the iridium(I) precursors with xenon difluoride.

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Homoleptische Carbonylkomplex‐Kationen der elektronenreichen Metalle: Bildung in supersauren Medien sowie spektroskopische und strukturelle Charakterisierung

Willner¹,

Aubke²

1997

Angewandte Chemie

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Homoleptische Carbonylkomplex‐Kationen der elektronenreichen Metalle der Gruppen 8 bis 12 sind die jüngsten Mitglieder der großen Familie der Carbonyl‐Übergangsmetall‐Derivate. Sie unterscheiden sich in vielen Aspekten von den typischen Metallcarbonylen. Sie entstehen durch Carbonylierung von Metallsalzen in Supersäuren wie Fluorsulfonsäure und “magischer Säure”, HSO3F/SbF5. Thermisch stabile Salze mit [Sb2F11]− als Gegenion werden aus Antimonpentafluorid als Reaktionsmedium erhalten. Sowohl das [Sb2F11]−‐Ion als auch supersaure Reaktionsmedium fanden in der metallorganischen Chemie der d‐Block‐Elemente bisher wenig Anwendung. Ohne Beispiel in der Metallcarbonylchemie sind auch die Koordinationsgeometrien der Kationen mit den Koordinationszahlen 4 (quadratisch‐planar) und 2 (linear). Die formalen Oxidationsstufen der Metalle und somit auch die Ladungen der Komplexkationen reichen von +1 bis +3, so daß CO an das Metall überwiegend σ‐gebunden ist und die C‐O‐Bindung stark polarisiert wird. Die geringe Metall → CO‐π‐Rückbindung und die positive Partialladung am C‐Atom äußern sich in langen M‐C‐Bindungen, kurzen C‐O‐Bindungen, hohen Wellenzahlen der CO‐Streckschwingungen (bis 2300 cm−1) und niedrigen 13C‐NMR‐Verschiebungen (bis δC = 121). Herausragende Beispiele für diese ungewöhnlichen homoleptischen Carbonylkomplex‐Kationen sind [Hg(CO)2]2+, das erste Carbonylkomplex‐Kation eines p‐Block‐Metalls. [Ir(CO)6]3+, das erste dreiwertige Carbonylkomplex‐Kation, und [Fe(CO)6]2+, das erste mehrfach geladene Carbonylkomplex‐Kation eines 3d‐Metalls. Mit diesem Übersichtsartikel wollen wir a) die Anfangsgeschichte kationischer Carbonylmetallverbindungen sowie Verfahren zu ihrer Synthese aufzeigen, b) eine Zusammenfassung des Gebiets der Carbonylkomplex‐Kationen geben, das sich in sehr kurzer Zeit rapide entwickelt hat, c) die strukturellen und spektroskopischen Eigenschaften der Metall‐CO‐Bindung diskutieren, d) die besondere Bedeutung, die den Reaktionsmedien und dem [Sb2F11]−‐Ion zukommt, herausstellen und e) auf neueste Ergebnisse und zukünftige Entwicklungen hinweisen.

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Fluorination of tetrairidium dodecacarbonyl

Cited by 20 publications

References 9 publications

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)₃(SO₃F)₃

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)₃(SO₃F)₃

Synthesis and characterisation of some iridium-carbonyl-fluoride complexes. Crystal structures of [IrF(CO){P(C6H4-2-CH3)3}2] and [IrF2(COD)py2][BF4]

Homoleptische Carbonylkomplex‐Kationen der elektronenreichen Metalle: Bildung in supersauren Medien sowie spektroskopische und strukturelle Charakterisierung

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Fluorination of tetrairidium dodecacarbonyl

Cited by 20 publications

References 9 publications

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)3(SO3F)3

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)3(SO3F)3

Synthesis and characterisation of some iridium-carbonyl-fluoride complexes. Crystal structures of [IrF(CO){P(C6H4-2-CH3)3}2] and [IrF2(COD)py2][BF4]

Homoleptische Carbonylkomplex‐Kationen der elektronenreichen Metalle: Bildung in supersauren Medien sowie spektroskopische und strukturelle Charakterisierung

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Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)₃(SO₃F)₃

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)₃(SO₃F)₃