Darstellung und Schwingungsspektren von Fluoro-Chloro-Iridaten(IV) einschließlich der Stereoisomeren / Preparation and Vibrational Spectra of Fluoro-Chloro-Iridates(IV) Including Stereoisomers

Tensfeldt, D.; Preetz, W.

doi:10.1515/znb-1984-0906

Cited by 12 publications

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“…Despite these developments, well-defined examples of Ir in the +IV oxidation state are still limited . These include inorganic hexahalogeno complexes and several organometallic compounds , with substituted phenyl or cyclopentadienyl ligands.…”

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Stabilization of Iridium(IV) by Monoanionic Dialkyldiarylguanidinato Ligands

Rohde

Lee

2009

J. Am. Chem. Soc.

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Electron-rich tris(guanidinato) complexes of Ir(III), [Ir{ArNC(NR(2))NAr}(3)] (where R = Me or Et; Ar = Ph or 4-MeC(6)H(4)), were synthesized from the respective [Ir{ArNC(NR(2))NAr}(C(8)H(14))(2)] precursors (C(8)H(14) = cis-cyclooctene), are air-sensitive, and can be electrochemically oxidized in two one-electron transfer steps. The first electron transfer is reversible and occurs at much lower potentials than typical for Ir(III). Chemical oxidation by [FeCp(2)]PF(6) afforded isolable, paramagnetic Ir(IV) compounds, [Ir{ArNC(NR(2))NAr}(3)]PF(6), which were characterized by analytical and spectroscopic methods and a single-crystal structure determination, demonstrating that Ir(IV) is accessible in a nitrogen-donor ligand environment.

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confidence: 99%

Stabilization of Iridium(IV) by Monoanionic Dialkyldiarylguanidinato Ligands

Rohde

Lee

2009

J. Am. Chem. Soc.

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“…Die Darstellung der Komplexe erfolgt entsprechend den Vorschriften in [6,7]. Man erha È lt dunkelrote Einkristalle von 1 und 2 in Form kleiner Kuben, indem man unter Argonatmospha È re langsam 1,1,2-Trifluortrichlorethan in eine Lo È sung des Komplexsalzes in Dichlormethan bei ±30°C diffundieren la È ût.…”

Section: Experimentelles A) Darstellungunclassified

Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse vonfac-(Et4N)[OsF3Cl3] undfac-(Et4N)[IrF3Cl3]

Lorenzen

Preetz

2000

Z. anorg. allg. Chem.

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Bei der vorsichtigen Oxidation der reinen Fluorochloroosmate(IV) oder ‐iridate(IV) mit BrF3 oder KBrF4 in Dichlormethan entstehen die gemischten fünfwertigen Komplexanionen fac‐[OsF3Cl3]– und fac‐[IrF3Cl3]–. Röntgenstrukturanalysen sind an Einkristallen von fac‐(Et4N)[OsF3Cl3] (1) (orthorhombisch, Raumgruppe Pbca, a = 11,225(5), b = 12,020(5), c = 21,837(5) Å, Z = 8) und fac‐(Et4N)[IrF3Cl3] (2) (orthorhombisch, Raumgruppe Pbca, a = 11,269(10), b = 12,049(1), c = 21,801(3) Å, Z = 8) durchgeführt worden. Unter Verwendung der röntgenographisch ermittelten Molekülparameter werden die registrierten IR‐ und Raman‐Spektren für das Anion von 1 und 2 durch Normalkoordinatenanalysen zugeordnet. Die Osmium‐Verbindung zeigt etwas größere Valenzkraftkonstanten als die Iridium‐Verbindung: fd(OsF) = 3,35, fd(IrF) = 3,25, fd(OsCl) = 2,35 und fd(IrCl) = 2,25 mdyn/Å.

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“…18 High-valent Ir complexes could also serve as oxygen atom transfer agents. 5 19,20 These include inorganic hexahalogeno complexes 21,22 and several organometallic compounds 5,[23][24][25][26][27] For a broader exploration of the chemistry of Ir IV , however, the availability of complexes with multidentate ligands based on organic heteroatom-donor frameworks would be of great advantage, as has been the case for other high-valent transition metal centers. 30,31 Although a series of stable complexes of the type [Ir IV X 4 L 2 ]; where X = Cl, Br and L = N-, P-, or S-donor ligand; were described two decades ago, the corresponding complexes with more than two heteroatom donors could not be obtained.…”

Section: Scheme 4 High-valent Ir In C−h Bond Activationmentioning

confidence: 99%

Tris(guanidinato)complexes of iridium and rhodium in the oxidation states +III and +IV

Lee¹

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Mononuclear [Ir{ArNC(NR 2)NAr}(C 8 H 14) 2 ] complexes (where R = Me or Et; Ar = Ph or 4-MeC 6 H 4 ; and C 8 H 14 = cis-cyclooctene) were synthesized from the neutral N,Ndialkyl-N′,N′′-diarylguanidines via deprotonation and transmetalation. As confirmed by single-crystal structure determination, the guanidinato(1−) ligands coordinate the lowvalent d 8 Ir I center in an N,N′-chelating binding mode, and the C−N distances of the CN 3 core suggest that these ligands function as stronger donors than related monoanionic, bidentate nitrogen-based ligands. In the reaction of the complexes with O 2 , new [Ir{ArNC(NR 2)NAr}] 3 complexes were identified among the products, suggesting a new route for their synthesis. Tris(guanidinato) complexes of Ir III , [Ir{ArNC(NR 2)NAr} 3 ] (R = Me or Et; Ar = Ph or 4-MeC 6 H 4), were synthesized and, as revealed by electrochemical measurements, can be oxidized reversibly at unusually low potentials. These potentials are even lower than those of other Ir III complexes with very electron-rich, trianonic ligand sets as, for example, in cyclometalated tris(2-pyridylphenyl), corrolato and tris(dithiocarbamato) complexes. Chemical oxidation by [FeCp 2 ]PF 6 afforded isolable, paramagnetic Ir IV compounds, [Ir{ArNC(NR 2)NAr} 3 ]PF 6 , which were characterized by elemental analysis, mass spectrometry, electronic absorption and EPR spectroscopy and X-ray crystallography. The reactivity of these Ir IV complexes toward mild inorganic and organic reductants and substrates with O−H bonds was investigated. Similar tris(guanidinato) complexes of Rh III , [Rh{ArNC(NR 2)NAr} 3 ] (R = Me or Et; Ar = Ph, 4-MeC 6 H 4 or 4-MeOC 6 H 4), were synthesized. These complexes also were oxidized reversibly at low potentials, as compared to the corresponding tris(amidinato) and tris(triazenido) complexes. Chemical oxidation by [FeCp 2 ]PF 6 afforded thermally unstable, paramagnetic Rh IV compounds, [Rh{ArNC(NR 2)NAr} 3 ]PF 6 , which were characterized by mass spectrometry and electronic absorption spectroscopy.

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Darstellung und Schwingungsspektren von Fluoro-Chloro-Iridaten(IV) einschließlich der Stereoisomeren / Preparation and Vibrational Spectra of Fluoro-Chloro-Iridates(IV) Including Stereoisomers

Abstract: The reaction of [IrCl6]2- with BrF3 generates the mixed complexes [IrFnCl6-n]2-, n = 1-5, of which the species with n = 2, 3, 4 are ds-configurated. Due to the stronger trans-effect of Cl as compared to F on treatment of [IrF5Cl]2- and cis-[IrF4Cl2]2- with SOCl2 Show more

Cited by 12 publications

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Stabilization of Iridium(IV) by Monoanionic Dialkyldiarylguanidinato Ligands

Stabilization of Iridium(IV) by Monoanionic Dialkyldiarylguanidinato Ligands

Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse vonfac-(Et4N)[OsF3Cl3] undfac-(Et4N)[IrF3Cl3]

Tris(guanidinato)complexes of iridium and rhodium in the oxidation states +III and +IV

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