Ketimido Metallophthalocyanines: An Approach to Phthalocyanine‐Supported Mononuclear High‐Valent Ruthenium Complexes

Huang, Jie‐Sheng; Wong, Kwok-Ming; Chan, S. C.; Tso, Ken Chi-Hang; Jiang, Tao; Che, Chi‐Ming

doi:10.1002/asia.201301109

Cited by 8 publications

(1 citation statement)

References 150 publications

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“…Aryl imido 3 also rapidly reacts with t BuNH 2 to afford the green diamagnetic Co III quinone imido complex [(TIMMN mes )Co III (NC 6 H 4 N t Bu)](PF 6 ) 2 ( 6 ) (Scheme , bottom). − Trivalent 6 is unstable in solution at room temperature and quickly decomposes into a complicated mixture of products. A quick 5-min reaction, carried out at −25 °C, followed by careful low-temperature workup, allowed for the isolation of 6 in 59% yield.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Reactivity of a Cobalt-Supported Singlet Nitrene

et al. 2023

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The synthesis, characterization, and reactivity of a series of cobalt terminal imido complexes supported by an Nanchored tripodal tris(carbene) chelate is described, including a Cosupported singlet nitrene. Reaction of the Co I precursor [(TIMMN mes )Co I ](PF 6 ) (TIMMN mes = tris- [2-(3-mesityl-imidazolin-2-ylidene)-methyl]amine) with p-methoxyphenyl azide yields a Co III imide [(TIMMN mes )Co III (NAnisole)](PF 6 ) (1). Treatment of 1 with 1 equiv of [FeCp 2 ](PF 6 ) at −35 °C affords a formal Co IV imido complex [(TIMMN mes )Co(NAnisole)](PF 6 ) 2 (2), which features a bent Co−N(imido)−C(Anisole) linkage. Subsequent one-electron oxidation of 2 with 1 equiv of AgPF 6 provides access to the tricationic cobalt imido complex [(TIMMN mes )Co-(NAnisole)](PF 6 ) 3 (3). All complexes were fully characterized, including single-crystal X-ray diffraction (SC-XRD) analyses, infrared (IR) vibrational, ultraviolet/visible (UV/vis) electronic absorption, multinuclear NMR, X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and high-energy-resolution fluorescence-detected X-ray absorption spectroscopy (HERFD XAS). Quantum chemical calculations provide additional insight into the electronic structures of all compounds. The dicationic Co IV imido complex 2 exhibits a doublet ground state with considerable imidyl character as a result of covalent Co−NAnisole bonding. At room temperature, 2 readily converts to a Co II amine complex involving intramolecular C−H bond amination. Electronically, tricationic complex 3 can be understood as a singlet nitrene bound to Co III with significant Co IV imidyl radical character. Verifying the pronounced electrophilicity, nucleophiles such as H 2 O and t BuNH 2 add to 3�analogous to the parent free nitrene�in the para position of the aromatic substituent, thus, clearly corroborating singlet nitrene-type reactivity.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Reactivity of a Cobalt-Supported Singlet Nitrene

et al. 2023

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[Fe(F₂₀TPP)Cl]‐Catalyzed Amination with Arylamines and {[Fe(F₂₀TPP)(NAr)](PhINAr)} Intermediate Assessed by High‐Resolution ESI‐MS and DFT Calculations

Liu

Chen

Tse

et al. 2014

Chemistry An Asian Journal

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Amination of CH bonds catalyzed by transition metal complexes via nitrene/imide insertion is an appealing strategy for CN bond formation, and the use of iminoiodinanes, or their in situ generated forms from 'PhI(OAc)2 +primary amides (such as sulfonamides, sulfamates, and carbamates)', as nitrogen sources for the amination reaction has been well documented. In this work, a 'metal catalyst+PhI(OAc)2 +primary arylamines' amination protocol has been developed using [Fe(F20 TPP)Cl] (H2 F20 TPP=meso-tetrakis(pentafluorophenyl)porphyrin) as a catalyst. This catalytic method is applicable for both intra- and intermolecular amination of sp(2) and sp(3) CH bonds (>27 examples), affording the amination products, including natural products such as rutaecarpine, in moderate-to-good yields. ESI-MS analysis and DFT calculations lend support for the involvement of {[Fe(F20 TPP)(NC6 H4 -p-NO2 )](PhI=NC6 H4 -p-NO2 )} + . intermediate in the catalysis.

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Density Functional Theory Calculations on Oxidative CC Bond Cleavage and NO Bond Formation of [Ru^II(bpy)₂(diamine)]²⁺ via Reactive Ruthenium Imide Intermediates

Guan

Law

Tse

et al. 2014

Chemistry A European J

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DFT calculations are performed on [Ru(II)(bpy)2(tmen)](2+) (M1, tmen = 2,3-dimethyl-2,3-butanediamine) and [Ru(II)(bpy)2(heda)](2+) (M2, head = 2,5-dimethyl-2,5-hexanediamine), and on the oxidation reactions of M1 to give the C-C bond cleavage product [Ru(II)(bpy)2(NH=CMe2)2](2+) (M3) and the N-O bond formation product [Ru(II)(bpy)2(ONCMe2CMe2NO)](2+) (M4). The calculated geometrical parameters and oxidation potentials are in good agreement with the experimental data. As revealed by the DFT calculations, [Ru(II)(bpy)2(tmen)](2+) (M1) can undergo oxidative deprotonation to generate Ru-bis(imide) [Ru(bpy)2(tmen-4 H)](+) (A) or Ru-imide/amide [Ru(bpy)2(tmen-3 H)](2+) (A') intermediates. Both A and A' are prone to C-C bond cleavage, with low reaction barriers (ΔG(≠)) of 6.8 and 2.9 kcal mol(-1) for their doublet spin states (2)A and (2)A', respectively. The calculated reaction barrier for the nucleophilic attack of water molecules on (2)A' is relatively high (14.2 kcal mol(-1)). These calculation results are in agreement with the formation of the Ru(II)-bis(imine) complex M3 from the electrochemical oxidation of M1 in aqueous solution. The oxidation of M1 with Ce(IV) in aqueous solution to afford the Ru(II)-dinitrosoalkane complex M4 is proposed to proceed by attack of the cerium oxidant on the ruthenium imide intermediate. The findings of ESI-MS experiments are consistent with the generation of a ruthenium imide intermediate in the course of the oxidation.

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Ketimido Metallophthalocyanines: An Approach to Phthalocyanine‐Supported Mononuclear High‐Valent Ruthenium Complexes

Cited by 8 publications

References 150 publications

Synthesis and Reactivity of a Cobalt-Supported Singlet Nitrene

Synthesis and Reactivity of a Cobalt-Supported Singlet Nitrene

[Fe(F₂₀TPP)Cl]‐Catalyzed Amination with Arylamines and {[Fe(F₂₀TPP)(NAr)](PhINAr)} Intermediate Assessed by High‐Resolution ESI‐MS and DFT Calculations

Density Functional Theory Calculations on Oxidative CC Bond Cleavage and NO Bond Formation of [Ru^II(bpy)₂(diamine)]²⁺ via Reactive Ruthenium Imide Intermediates

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Ketimido Metallophthalocyanines: An Approach to Phthalocyanine‐Supported Mononuclear High‐Valent Ruthenium Complexes

Cited by 8 publications

References 150 publications

Synthesis and Reactivity of a Cobalt-Supported Singlet Nitrene

Synthesis and Reactivity of a Cobalt-Supported Singlet Nitrene

[Fe(F20TPP)Cl]‐Catalyzed Amination with Arylamines and {[Fe(F20TPP)(NAr)](PhINAr)} Intermediate Assessed by High‐Resolution ESI‐MS and DFT Calculations

Density Functional Theory Calculations on Oxidative CC Bond Cleavage and NO Bond Formation of [RuII(bpy)2(diamine)]2+ via Reactive Ruthenium Imide Intermediates

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[Fe(F₂₀TPP)Cl]‐Catalyzed Amination with Arylamines and {[Fe(F₂₀TPP)(NAr)](PhINAr)} Intermediate Assessed by High‐Resolution ESI‐MS and DFT Calculations

Density Functional Theory Calculations on Oxidative CC Bond Cleavage and NO Bond Formation of [Ru^II(bpy)₂(diamine)]²⁺ via Reactive Ruthenium Imide Intermediates