Half‐Sandwich Iridium Complexes Bearing a Diprotic Glyoxime Ligand: Structural Diversity Induced by Reversible Deprotonation

Takamura, Taishin; Harada, Takuya; Furuta, Tatsuro; Ikariya, Takao; Kuwata, Shigeki

doi:10.1002/asia.201901276

“…Spectroscopic characterization by 1 H NMR (see SI, Figure S23) is in agreement with the prior literature report. 45 Yield = 90% (115 mg). Synthesis of dpgIr-Cl.…”

Section: General Considerationsmentioning

confidence: 99%

“…These complexes are [Cp*Ir(dmg)Cl]Cl, [Cp*Rh(dpg)Cl]PF6, and [Cp*Ir(dpg)Cl]Clwhere dmg is κ 2 -dimethylglyoxime and dpg is κ 2 -diphenylglyoxime. Notably, in the course of completing the work described here, Kuwata and co-workers reported the synthesis and characterization of [Cp*Ir(dmg)Cl]Cl 45.…”

mentioning

confidence: 99%

Incorporation of [CpRh] and [CpIr] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation

Kumar¹,

King²,

Day³

et al. 2021

Preprint

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<a></a>Synthesis of multimetallic compounds can enable placement of two or more metals in close proximity, but efforts in this area are often hindered by reagent incompatibilities and lack of selectivity. Here, we show that organometallic half-sandwich [Cp*M] (M = Rh, Ir) fragments (where Cp* is η5-pentamethylcyclopentadienyl) can be cleanly installed into metallomacrocyclic structures based on the workhorse diimine-monooxime-monooximato ligand system. Six new heterobimetallic compounds have been prepared to explore this synthetic chemistry, which relies on in situ protonolysis reactivity with precursor Ni(II) or Co(III) monometallic complexes in the presence of suitable [Cp*M] species. Solid-state X-ray diffraction studies confirm installation of the [Cp*M] fragments into the metallomacrocyles via effective chelation of the Rh(III) and Ir(III) centers by the nascent dioximato site. Contrasting with square-planar Ni(II) centers, the Co(III) centers prefer octahedral geometry in the heterobimetallic compounds, promoting bridging ligation of acetate across the two metals. Spectroscopic and electrochemical studies reveal subtle influences of the metals on each other’s properties, consistent with the moderate M′•••M distances of ca. 3.6–3.7 Å in the modular compounds. The [Co,Rh] complex was found to catalyze hydrogenation of p-trifluoromethylbenzaldehyde to p-trifluoromethylbenzyl alcohol more cleanly than a 1:1 mixture of the individual monometallic precursor complexes, suggesting that this family of heterobimetallic complexes could be useful in future studies of multimetallic chemistry, especially in light of the starring role of other [Cp*M] complexes in diverse catalytic systems.

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“…Notably, in the course of completing the work described here, Kuwata and co-workers reported the synthesis and characterization of [Cp*Ir(dmg)Cl]Cl. 45 Synthesis of dmgIr-Cl. A solution of [Cp*IrCl2]2 (100 mg, 0.12 mmol) in dichloromethane was added dropwise to a solution of dimethylgly-(29 mg, 0.25 mmol) in MeOH.…”

Section: Synthesis and Characterization Of Monometallic Cobalt Complexes And Heterobimetallic Complexesmentioning

confidence: 99%

“…Spectroscopic characterization by 1 H NMR (see SI, Figure S23) is in agreement with the prior literature report. 45 Yield = 90% (115 mg). Synthesis of dpgIr-Cl.…”

Section: Synthesis and Characterization Of Monometallic Cobalt Complexes And Heterobimetallic Complexesmentioning

confidence: 99%

Incorporation of [CpRh] and [CpIr] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation

Kumar¹,

King²,

Day³

et al. 2021

Preprint

0

View full text Add to dashboard Cite

<a></a>Synthesis of multimetallic compounds can enable placement of two or more metals in close proximity, but efforts in this area are often hindered by reagent incompatibilities and lack of selectivity. Here, we show that organometallic half-sandwich [Cp*M] (M = Rh, Ir) fragments (where Cp* is η5-pentamethylcyclopentadienyl) can be cleanly installed into metallomacrocyclic structures based on the workhorse diimine-monooxime-monooximato ligand system. Six new heterobimetallic compounds have been prepared to explore this synthetic chemistry, which relies on in situ protonolysis reactivity with precursor Ni(II) or Co(III) monometallic complexes in the presence of suitable [Cp*M] species. Solid-state X-ray diffraction studies confirm installation of the [Cp*M] fragments into the metallomacrocyles via effective chelation of the Rh(III) and Ir(III) centers by the nascent dioximato site. Contrasting with square-planar Ni(II) centers, the Co(III) centers prefer octahedral geometry in the heterobimetallic compounds, promoting bridging ligation of acetate across the two metals. Spectroscopic and electrochemical studies reveal subtle influences of the metals on each other’s properties, consistent with the moderate M′•••M distances of ca. 3.6–3.7 Å in the modular compounds. The [Co,Rh] complex was found to catalyze hydrogenation of p-trifluoromethylbenzaldehyde to p-trifluoromethylbenzyl alcohol more cleanly than a 1:1 mixture of the individual monometallic precursor complexes, suggesting that this family of heterobimetallic complexes could be useful in future studies of multimetallic chemistry, especially in light of the starring role of other [Cp*M] complexes in diverse catalytic systems.

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“…The protons from NH groups appeared at 8.75 ppm and those from oximic groups at 10.92 ppm, all as large singlets. The tertiary carbon atoms from aromatic rings were registered at 117.92 and 130.45 ppm, quaternary at 123 19. and 144.55 ppm.…”

mentioning

confidence: 99%

Novel vic-dioximes: synthesis, structure characterization, and antimicrobial activity evaluation

2021

Turk J Chem

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The vic-dioximes are compounds with various industrial uses and scientific applications. Many coordination compounds have been synthesized based on vicdioximes. This study presents the synthesis and full characterization of two vicdioximes based on dichloroglyoxime, p-aminobenzoic acid and p-aminotoluene. Their structures were proved by IR, 1 H, 13 C and 15 N NMR spectral analysis and single crystal X-ray diffraction. One of the reported vic-dioximes, bis(di-p-aminotoluene)glyoxime mono-p-aminotoluene trihydrate showed good to moderate antimicrobial activity against both non-pathogenic Gram-positive and Gram-negative bacteria (Bacillus subtilis and Pseudomonas fluorescens), phytopathogenic (Xanthomonas campestris, 2 Erwinia amylovora, E. carotovora) and the fungi (Candida utilis and Saccharomyces cerevisiae) at MIC -70-150 μg/mL.

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Half‐Sandwich Iridium Complexes Bearing a Diprotic Glyoxime Ligand: Structural Diversity Induced by Reversible Deprotonation

Cited by 8 publications

References 52 publications

Incorporation of [CpRh] and [CpIr] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation

Incorporation of [CpRh] and [CpIr] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation

Incorporation of [CpRh] and [CpIr] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation

Novel vic-dioximes: synthesis, structure characterization, and antimicrobial activity evaluation

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Half‐Sandwich Iridium Complexes Bearing a Diprotic Glyoxime Ligand: Structural Diversity Induced by Reversible Deprotonation

Cited by 8 publications

References 52 publications

Incorporation of [Cp*Rh] and [Cp*Ir] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation

Incorporation of [Cp*Rh] and [Cp*Ir] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation

Incorporation of [Cp*Rh] and [Cp*Ir] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation

Novel vic-dioximes: synthesis, structure characterization, and antimicrobial activity evaluation

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Product

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Incorporation of [CpRh] and [CpIr] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation

Incorporation of [CpRh] and [CpIr] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation

Incorporation of [CpRh] and [CpIr] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation