Direct functionalization of the cyclometalated 2-(2′-pyridyl)phenyl ligand bound to iridium(III)

Cheung, Ka-Man; Zhang, Qian‐Feng; Chan, Ka Man; Lam, Michael; Williams, Ian D.; Leung, Wa‐Hung

doi:10.1016/j.jorganchem.2005.03.013

Cited by 22 publications

(13 citation statements)

References 35 publications

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“…The Ir–N distances (av. 2.091(4) Å) are similar to those in [Ir(Br‐ppy) 2 (dtbpy)] + (Br‐ppy=4‐bromo‐2‐(2‐pyridyl)phenyl; 2.129(9) Å) 22. The Ir–CH 3 and Ir–CH 2 SiMe 3 distances (av.…”

Section: Resultssupporting

confidence: 60%

Iridium(III) Silyl Alkyl and Iridacyclic Compounds Supported by 4,4′‐Di‐tert‐butyl‐2,2′‐bipyridyl

Lee

Williams

et al. 2006

Chemistry A European J

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Treatment of IrCl(3)x H(2)O with one equivalent of 4,4'-di-tert-butyl-2,2'-bipyridyl (dtbpy) in N,N-dimethylformamide (dmf) afforded [IrCl(3)(dmf)(dtbpy)] (1). Alkylation of 1 with Me(3)SiCH(2)MgCl resulted in C--Si cleavage of the Me(3)SiCH(2) group and formation of the Ir(III) silyl dialkyl compound [Ir(CH(2)SiMe(3))(dtbpy)(Me)(SiMe(3))] (2), which reacted with tBuNC to afford [Ir(tBuNC)(CH(2)SiMe(3))(dtbpy)(Me)(SiMe(3))] ([2(tBuNC)]). Reaction of 2 with phenylacetylene afforded dimeric [{Ir(C[triple chemical bond]CPh)(dtbpy)(SiMe(3))}(2)(mu-C[triple chemical bond]CPh)(2)] (3), in which the bridging PhC[triple chemical bond]C(-) ligands are bound to Ir in a mu-sigma:pi fashion. Alkylation of 1 with PhMe(2)CCH(2)MgCl afforded the cyclometalated compound [Ir(dtbpy)(CH(2)CMe(2)C(6)H(4))(2-C(6)H(4)CMe(3))] (4), which features an agostic interaction between the Ir center and the 2-tert-butylphenyl ligand. The cyclic voltammogram of 4 in CH(2)Cl(2) shows a reversible Ir(IV)-Ir(III) couple at about 0.02 V versus ferrocenium/ferrocene. Oxidation of 4 in CH(2)Cl(2) with silver triflate afforded an Ir(IV) species that exhibits an anisotropic electron paramagnetic resonance (EPR) signal in CH(2)Cl(2) glass at 4 K with g( parallel)=2.430 and g( perpendicular)=2.110. Protonation of 4 with HCl and p-toluenesulfonic acid (HOTs) afforded [{Ir(dtbpy)(CH(2)CMe(2)Ph)Cl}(2)(mu-Cl)(2)] (5) and [Ir(dtbpy)(CH(2)CMe(2)Ph)(OTs)(2)] (6), respectively. Reaction of 5 with Li[BEt(3)H] gave the cyclometalated complex [{Ir(dtbpy)(CH(2)CMe(2)C(6)H(4))}(2)(mu-Cl)(2)] (7). Reaction of 4 with tetracyanoethylene in refluxing toluene resulted in electrophilic substitution of the iridacycle by C(2)(CN)(3) with formation of [Ir(dtbpy)(CH(2)CMe(2)C(6)H(3){4-C(2)(CN)(3)})(2-C(6)H(4)CMe(3))] (8). Reaction of 4 with diethyl maleate in refluxing toluene gave the iridafuran compound [Ir(dtbpy)(CH(2)CMe(2)C(6)H(4)){kappa(2)(C,O)-C(CO(2)Et)CH(CO(2)Et)}] (9). Treatment of 9 with 2,6-dimethylphenyl isocyanide (xylNC) led to cleavage of the iridafuran ring and formation of [Ir(dtbpy)(CH(2)CMe(2)C(6)H(4)){C(CO(2)Et)CH(CO(2)Et)}(xylNC)] (10). Protonation of 9 with HBF(4) afforded the dinuclear neophyl complex [(Ir(dtbpy)(CH(2)CMe(2)Ph){kappa(2)(C,O)-C(CO(2)Et)CH(CO(2)Et)})(2)][BF(4)](2) (11). The solid-state structures of complexes 2-5 and 8-11 have been determined.

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Section: Resultssupporting

confidence: 60%

Iridium(III) Silyl Alkyl and Iridacyclic Compounds Supported by 4,4′‐Di‐tert‐butyl‐2,2′‐bipyridyl

Lee

Williams

et al. 2006

Chemistry A European J

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“…[44] Williams et al treated the dinuclear Ru-Ir complex 67 with two equivalents of NBS in acetonitrile at room temperature for 18 h to give the building block 68. The latter undergoes cross-coupling reactions with different partners, allowing the preparation of tetrametallic assemblies such as 69 (Scheme 15).…”

Section: Methodsmentioning

confidence: 99%

“…[44] In the bromination of 65 also [{Ir(4-Br-ppy)(py)(m-Br)} 2 ] was formed as a minor product, which could be separated by fractional crystallization. Both 64 and 66 have been successfully employed in …”

Section: S-aryl Complexesmentioning

confidence: 99%

Organic Transformations on σ‐Aryl Organometallic Complexes

et al. 2007

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This work reviews recent developments in the field of organic transformations on sigma-aryl organometallic complexes. The general notion that M--C sigma bonds are kinetically labile, highly reactive, and incompatible with typical reaction conditions met in organic synthesis has limited the use of these synthetic strategies thus far. However, organic transformations on metal-bound sigma-aryl fragments are being used more and more by chemists in both industry and academia. In this Review, emphasis is put on the synthetic methods applied in this field up to now. The simplicity and generally good yields of these methods are very attractive for the construction of functionalized organometallic building blocks that are potentially useful as photochemical molecular devices, biosensors and -conjugates, or molecular switches. Thus, this Review has been tailored for a broader audience with the aim of encouraging the application of these strategies.

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“…haben die Ir III ‐Komplexe [{Ir(ppy) 2 (μ‐Cl)} 2 ] ( 63 ) und [Ir(ppy) 2 (4,4′‐ t Bu‐2,2′‐bpy)](OTf) ( 65 ) (ppy=2‐Phenylpyridin) mit Pyridiniumtribromid in Gegenwart von Eisenpulver bromiert, wodurch die Komplexe [{Ir(4‐Br‐ppy)(μ‐Br)} 2 ] ( 64 ) bzw. [Ir(4‐Brppy) 2 (4,4′‐ t Bu‐2,2′‐bpy)](OTf) ( 66 ) erhalten wurden (Schema ) 44. Bei der Bromierung von 65 wurde auch [{Ir(4‐Br‐ppy)(py)(μ‐Br)} 2 ] als Nebenprodukt gebildet, das durch fraktionierende Kristallisation abgetrennt werden konnte.…”

Section: Regioselektive Elektrophile Substitution Von Heterocyclisunclassified

“…Bei der Bromierung von 65 wurde auch [{Ir(4‐Br‐ppy)(py)(μ‐Br)} 2 ] als Nebenprodukt gebildet, das durch fraktionierende Kristallisation abgetrennt werden konnte. Sowohl 64 als auch 66 wurden in anschließenden Kreuzkupplungen mit Arylboronsäuren, Ethinylstannan und Butinol verwendet 44…”

Section: Regioselektive Elektrophile Substitution Von Heterocyclisunclassified

Organische Umsetzungen an metallorganischen σ‐Aryl‐Komplexen

et al. 2007

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Dieser Aufsatz gibt einen Überblick über neue Entwicklungen auf dem Gebiet der metallvermittelten organischen Umsetzungen an metallorganischen σ‐Aryl‐Komplexen. Die allgemeine Vorstellung, dass M‐C‐σ‐Bindungen kinetisch labil, hoch reaktiv und unvereinbar mit typischen Reaktionsbedingungen der organischen Synthese sind, hat die Anwendung dieser Synthesestrategien bisher eingeschränkt. Allerdings werden metallvermittelte organische Umsetzungen an metallgebundenen σ‐Aryl‐Fragmenten immer häufiger in industriellen und Laborsynthesen eingesetzt. Die Einfachheit und im Allgemeinen guten Ausbeuten dieser Methoden sind sehr attraktiv für den Aufbau funktionalisierter metallorganischer Bausteine, die als photochemische molekulare Funktionseinheiten, Biosensoren und ‐konjugate sowie molekulare Schalter genutzt werden könnten. Dieser Aufsatz richtet sich daher an eine breitere Leserschaft und soll zum Gebrauch dieser Strategien ermutigen.

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Direct functionalization of the cyclometalated 2-(2′-pyridyl)phenyl ligand bound to iridium(III)

Cited by 22 publications

References 35 publications

Iridium(III) Silyl Alkyl and Iridacyclic Compounds Supported by 4,4′‐Di‐tert‐butyl‐2,2′‐bipyridyl

Iridium(III) Silyl Alkyl and Iridacyclic Compounds Supported by 4,4′‐Di‐tert‐butyl‐2,2′‐bipyridyl

Organic Transformations on σ‐Aryl Organometallic Complexes

Organische Umsetzungen an metallorganischen σ‐Aryl‐Komplexen

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