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

Sau, Yiu‐Keung; Lee, Hung-Kay; Williams, Ian D.; Leung, Wa‐Hung

doi:10.1002/chem.200600562

Cited by 21 publications

(31 citation statements)

References 79 publications

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“…). [6] Thus, it seems reasonable to assume that the Ag I oxidation of 8 resulted in a transient Ir III -thiyl radical cation species that dimerized by formation of an S-S disulfide bond.…”

Section: Iridacyclic Thiolate Complexesmentioning

confidence: 99%

“…Few stable Ir IV alkyls and aryls have been isolated, [4,5] presumably because of the stability of low-spin d 6 Ir III compounds, which renders their oxidation difficult. Recently, we synthesized the irida(III)cycle [Ir(dtbpy){CH 2 CMe 2 -C c 6 H 4 (Ir-C c )}(C 6 H 4 tBu-2)] (dtbpy = 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl) (1) by alkylation of [Ir(dtbpy)Cl 3 (dmf)] (dmf = N,N-dimethylformamide) with PhMe 2 CCH 2 MgCl.…”

Section: Introductionmentioning

confidence: 99%

“…Compound 1 could be oxidized reversibly to an Ir IV species, which was found to decompose in solutions to give the Ir III starting material. [6] In an attempt to enhance the stability of the Ir IV (9). The solid-state structures of compounds 2, 3, 4, 7, and 9 were determined.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Structures, and Oxidation of Iridium(III) Alkyl Compounds Containing Thiolate and Dithiolate Ligands

Chan

Zhang

et al. 2008

Eur J Inorg Chem

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Treatment of [Ir(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}(C6H4tBu‐2)] (1) (dtbpy = 4,4′‐di‐tert‐butyl‐2,2′‐bipyridyl) with the dichalcogenides R2Q2 in refluxing toluene afforded the chalcogenolate‐bridged dinuclear complexes [Ir(dtbpy) {CH2CMe2Cc6H4(Ir–Cc)}]2(μ‐QR)2 [RQ = pTolS (2), PhSe (3)]. Similarly, heating a solution of [Rh(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}(CH2CMe2Ph)] and p‐tolyl sulfide in toluene at reflux gave [Rh(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}]2(μ‐SpTol)2 (4). Treatment of [Ir(dtbpy)(CH2CMe2Ph)Cl]2(μ‐Cl)2 with Na(Sxyl) (xyl = 2,6‐dimethylphenyl) and Na2(S∧S) afforded [Ir(dtbpy)(CH2CMe2Ph)(Sxyl)2]2 (5) and [Ir(dtbpy)(CH2CMe2Ph)(S∧S)]2 {S∧S2– = maleonitriledithiolate (6), toluene‐3,4‐dithiolate (7), benzene‐1,2‐dithiolate (8)}. Oxidation of compound 8 with AgOTf (OTf– = triflate) resulted in dimerization of the bdt2– ligand by S–S bond formation and the isolation of [Ir2(dtbpy)2(CH2Me2Ph)2{(bdt)2}][OTf]2 (9). The solid‐state structures of compounds 2, 3, 4, 7, and 9 were determined. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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“…). [6] Thus, it seems reasonable to assume that the Ag I oxidation of 8 resulted in a transient Ir III -thiyl radical cation species that dimerized by formation of an S-S disulfide bond.…”

Section: Iridacyclic Thiolate Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis, Structures, and Oxidation of Iridium(III) Alkyl Compounds Containing Thiolate and Dithiolate Ligands

Chan

Zhang

et al. 2008

Eur J Inorg Chem

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“…Reaction of complex 2 with 2-phenylpyridine resulted in cyclometalation of 2-phenylpyridine, whereas that with 4-(2-pyridyl)benzaldehyde led to decarbonylation of the formyl group. Cationic Ir and Rh alkyl complexes 7 and 8 containing the noncoordinating [4] and NaBAr [19] were synthesized as described elsewhere. Atom labeling schemes for the metallacycles in cyclometalated complexes and the ppyH and dtbpy ligands are shown below.…”

Section: Discussionmentioning

confidence: 99%

“…[3,4] We found that the alkylation of [Rh(dtbpy)-Cl 3 (dmf)] (dmf = N,N-dimethylformamide) with Me 2 CCH 2 PhMgCl afforded the neophyl complex [Rh(dtbpy)(κ 2 -C,CЈ-CH 2 CMe 2 C 6 H 4 )(CH 2 CMe 2 Ph)]…”

Section: Introductionmentioning

confidence: 99%

C–H Activation with Iridium(III) and Rhodium(III) Alkyl Complexes Containing a 2,2′‐Bipyridyl Ligand

Chan

Huang

et al. 2010

Eur J Inorg Chem

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Heating [Rh(dtbpy)(κ2‐C,C′‐CH2CMe2C6H4)(CH2CMe2Ph)] (1; dtbpy = 4,4′‐di‐tert‐butyl‐2,2′‐bipyridyl) in p‐xylene at 110 °C resulted in the formation of the 2‐tert‐butylphenyl complex [Rh(dtbpy)(κ2‐C,C′‐CH2CMe2C6H4)(C6H4tBu‐2)] (3). Treatment of complex 1 with diethyl phosphite gave the phosphito‐bridged dimer [Rh(dtbpy)(κ2‐C,C′‐CH2CMe2C6H4){P(O)(OEt)2}]2 (4). Refluxing [Ir(dtbpy)(κ2‐C,C′‐CH2CMe2C6H4)(C6H4tBu‐2)] (2) with 2‐phenylpyridine (ppyH) and 4‐(2‐pyridyl)benzaldehyde in toluene followed by column chromatography afforded [Ir(dtbpy)(CH2CMe2Ph)Cl(κ2‐N,C‐ppy)] (5) and the carbonyl complex [Ir(dtbpy)(CH2CMe2Ph)(CO)(R)] (6) [R = 4‐(2‐pyridyl)phenyl], respectively. Anion metathesis of [M(dtbpy)(CH2CMe2Ph)(H2O)(OTs)2] with NaBArF4 [ArF = 3,5‐(CF3)2C6H3] afforded cationic [M(dtbpy)(CH2CMe2Ph)(H2O)(μ‐OTs)]2[BArF4]2 [M = Rh (7), Ir (8)] that are capable of catalyzing H/D exchange of tetrahydrofuran by using D2O as the deuterium source. The crystal structures of complexes 4–7 were determined.

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Significant Self‐Acceleration Effects of Nitrile Additives in the Rhodium‐Catalyzed Conversion of Aldoximes to Amides: A New Mechanistic Aspect

Kim

Lee

et al. 2009

Adv Synth Catal

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It was found that the catalytic activity of rhodium complexes was highly sensitive to the type of N-heterocyclic carbene (NHC) ligands in the conversion of aldoximes to amides. Among those species examined, the (cyclooctadiene)rhodium chloride-carbene complex RhACl exhibited the highest reactivity when it was employed in combination with a Brønsted acid, thus allowing mild reaction conditions. A significant rate acceleration effect resulting from the addition of nitrile additives was also observed. With the new protocol, the substrate scope of aldoximes has been widely expanded to include sterically congested and electronically varied derivatives. On the basis of detailed mechanistic studies, it is proposed that the reaction proceeds mainly via intramolecular electrophilic addition of aldoxime to rhodium-bound nitrile, which is different from the generally postulated two-step route: dehydration of aldoxime to nitrile followed by hydration of the latter intermediate.

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

Cited by 21 publications

References 79 publications

Synthesis, Structures, and Oxidation of Iridium(III) Alkyl Compounds Containing Thiolate and Dithiolate Ligands

Synthesis, Structures, and Oxidation of Iridium(III) Alkyl Compounds Containing Thiolate and Dithiolate Ligands

C–H Activation with Iridium(III) and Rhodium(III) Alkyl Complexes Containing a 2,2′‐Bipyridyl Ligand

Significant Self‐Acceleration Effects of Nitrile Additives in the Rhodium‐Catalyzed Conversion of Aldoximes to Amides: A New Mechanistic Aspect

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