N,N'-Disubstituted-1-amino-7-imino-1,3,5-cycloheptatrienes, a Non-classical Aromatic System

Brasen, Wallace R.; Holmquist, H. E.; Benson, R. E.

doi:10.1021/ja01475a031

Cited by 53 publications

(22 citation statements)

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“…12 Following the literature procedure, bromination occurred selectively in the 5-position giving the bromoarene in high yield. 13 Nucleophilic displacement proceeded smoothly and delivered the desired ligand 4 in an overall yield of 89% from 3. The synthesis of the zinc complex 2 was equally high yielding when the ligand was reacted with ZnMe 2 in toluene.…”

Section: Resultsmentioning

confidence: 96%

Electronic modification of an aminotroponiminate zinc complex leading to an increased reactivity in the hydroamination of alkenes

et al. 2008

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Section: Resultsmentioning

confidence: 96%

Electronic modification of an aminotroponiminate zinc complex leading to an increased reactivity in the hydroamination of alkenes

et al. 2008

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“…After initial reports on the functionalization of the C 7 ligand backbone in the 5‐position via electrophilic aromatic substitution,, this type of reaction has recently been investigated in further detail . Bromination proceeds smoothly and in excellent yields (90 %),, , while other substituents can be introduced only with lower yields of 19–43 % [Scheme , E = Br, I, N 2 Aryl, NO 2 , COMe, C 2 (CN) 3 ] , , . The bromo‐substituted compound 9‐Br can be subjected to nucleophilic aromatic substitution to give 10‐Nu in excellent yields (92–99 %) {Scheme : Nu = SPh, S[3,5‐C 6 H 3 (CF 3 ) 2 ], SePh, TePh; Nu = S(O)Ph with one additional step} .…”

Section: Ligand Synthesismentioning

confidence: 99%

New Perspectives for Aminotroponiminates: Coordination Chemistry, Redox Behavior, Cooperativity, and Catalysis

Hanft

Lichtenberg

2018

Eur J Inorg Chem

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Aminotroponiminates (ATIs) are monoanionic ligands with an N,N‐binding pocket and a rigid, planar, unsaturated, C7‐ring as a ligand backbone. Recent findings show that this ligand backbone can play an active role in coordination chemistry, redox reactions, and ligand‐centered reactivity of ATI complexes. Based on these results, ATIs have been recognized as redox‐active and cooperative ligands, which has implications for existing and potential future applications of ATI compounds in synthesis, catalysis, and materials science. The catalytic applications of ATI complexes are summarized in this Microreview, including results from the fields of hydroamination, epoxidation, cyanosilylation, ε‐caprolactone‐, olefin‐, epoxide‐, and epoxide/CO2 (co‐)polymerization as well as electron transfer catalysis. Furthermore, recent advances in the use of ATI ligands for stabilizing heavy analogs of carbon oxo compounds are showcased.

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“…Functionalisations in the C5 position in the ATI backbone of metal‐free ligands are possible by an electrophilic aromatic substitution and have granted access to a broad variety of aminotroponimines. [ 12a , 12c , 12e ] The transfer of a sterically demanding Ph 3 C group by reaction of the 5‐NO 2 ‐ATI complex 7 with Ph 3 CCl describes the first direct electrophilic aromatic substitution on an ATI complex. [16] Because the abstraction of a proton is required during the reaction, the sodium base NaH was employed in the rational synthesis of 11 .…”

Section: Resultsmentioning

confidence: 99%

Aminotroponiminates: Impact of the NO₂ Functional Group on Coordination, Isomerisation, and Backbone Substitution

Hanft

Rottschäfer

Wieprecht

et al. 2021

Chemistry A European J

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Aminotroponiminate (ATI) ligands are a versatile class of redox-active and potentially cooperative ligands with a rich coordination chemistry that have consequently found a wide range of applications in synthesis and catalysis. While backbone substitution of these ligands has been investigated in some detail, the impact of electron-withdrawing groups on the coordination chemistry and reactivity of ATIs has been little investigated. We report here Li, Na, and K salts of an ATI ligand with a nitro-substituent in the backbone. It is demonstrated that the NO 2 group actively contributes to the coordination chemistry of these complexes, effectively com-peting with the N,N-binding pocket as a coordination site. This results in an unprecedented E/Z isomerisation of an ATI imino group and culminates in the isolation of the first "naked" (i. e., without directional bonding to a metal atom) ATI anion. Reactions of sodium ATIs with silver(I) and tritylium salts gave the first N,N-coordinated silver ATI complexes and unprecedented backbone substitution reactions. Analytical techniques applied in this work include multinuclear (VT-) NMR spectroscopy, single-crystal X-ray diffraction analysis, and DFT calculations.

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N,N'-Disubstituted-1-amino-7-imino-1,3,5-cycloheptatrienes, a Non-classical Aromatic System

Cited by 53 publications

References 0 publications

Electronic modification of an aminotroponiminate zinc complex leading to an increased reactivity in the hydroamination of alkenes

Electronic modification of an aminotroponiminate zinc complex leading to an increased reactivity in the hydroamination of alkenes

New Perspectives for Aminotroponiminates: Coordination Chemistry, Redox Behavior, Cooperativity, and Catalysis

Aminotroponiminates: Impact of the NO₂ Functional Group on Coordination, Isomerisation, and Backbone Substitution

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N,N'-Disubstituted-1-amino-7-imino-1,3,5-cycloheptatrienes, a Non-classical Aromatic System

Cited by 53 publications

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Electronic modification of an aminotroponiminate zinc complex leading to an increased reactivity in the hydroamination of alkenes

Electronic modification of an aminotroponiminate zinc complex leading to an increased reactivity in the hydroamination of alkenes

New Perspectives for Aminotroponiminates: Coordination Chemistry, Redox Behavior, Cooperativity, and Catalysis

Aminotroponiminates: Impact of the NO2 Functional Group on Coordination, Isomerisation, and Backbone Substitution

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Aminotroponiminates: Impact of the NO₂ Functional Group on Coordination, Isomerisation, and Backbone Substitution