Molecular and crystal structure of p-benzoquinone-N,N?-bis-methylsulfonyldiimine

Shvets, A. E.; Mishnev, A. F.; Bleidelis, Ya. Ya.

doi:10.1007/bf00753286

Cited by 2 publications

(3 citation statements)

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“…In agreement with the fact that both 5 and 6 are ESR inactive, the intramolecular distances in both compounds fall into patterns consistent with a closed-shell quinoid formulation. The variation in the C−C bonds is nonetheless not quite as pronounced as in, for example, p -benzoquinone- N , N ‘-bis(methylsulfonyldiimine), 7 . The pattern is, indeed, very similar to that observed in the 1,4-phenylene bridged bis(1,3,2,4-dithiadiazolyl) 8 , which exists in the solid state as an associated diradical.…”

Section: Resultsmentioning

confidence: 58%

Benzo-Bridged Bis(1,2,3-dithiazoles) and Their Selenium Analogues. Preparation, Molecular and Electronic Structures, and Redox Chemistry

et al. 1997

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The condensation of diaminobenzenedithiol with sulfur monochloride leads to the chloride salt of the radical cation of 3,6-dichlorobenzo[1,2-d:4,5-d‘]bis(1,2,3-dithiazole), dichloro-[BB-123-DTA][Cl], which can be reduced to neutral dichloro-[BB-123-DTA] with triphenylantimony. A similar condensation with selenium tetrachloride leads, upon reduction, to the corresponding bis(1,2,3-thiaselenazole) dichloro-[BB-123-TSA]. The crystal and molecular structures of both compounds have been determined by X-ray diffraction. Both compounds, which are formally antiaromatic 16π-systems, exhibit internal bond lengths consistent with a quinoid formulation. The radical cations of both rings have been characterized by ESR spectroscopy; for dichloro-[BB-123-DTA]+ g = 2.0114 and a N = 0.201 mT, while for dichloro-[BB-123-TSA]+ g = 2.021 and a N = 0.44 mT. Further oxidation of both rings affords the corresponding dications, both of which have been characterized crystallographically as their AlCl4 - salts. The structural features of these compounds are consistent with those expected for dithiazolylium (or thiaselenazolylium) derivatives. The structure and redox chemistry of the benzo[1,2-d:4,5-d‘]bis(1,2,3-dithiazole) framework is discussed in the light of the results of ab initio calculations.

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Section: Resultsmentioning

confidence: 58%

Benzo-Bridged Bis(1,2,3-dithiazoles) and Their Selenium Analogues. Preparation, Molecular and Electronic Structures, and Redox Chemistry

et al. 1997

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“…33 Notably, the redox potential for the t Bu))], 11 p-benzoquinone, 47 p-benzoquinone monoxime, 48 and p-benzoquinonediimine. 49 There are two crystallographically independent molecules in the unit cell of 3. The bond distances and angles reported herein are the averages of the two molecules.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Bond metrics of [(TIMEN mes )Co III (NAnisole)](BPh 4 ), 1 , 2 , 3 , [(TIMMN mes )Co III ( • NMes)](PF 6 ) 2 , and copper nitrene [( EMind L)Cu(N(C 6 H 4 t Bu))], p -benzoquinone, p -benzoquinone monoxime, and p -benzoquinonediimine . There are two crystallographically independent molecules in the unit cell of 3 .…”

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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Molecular and crystal structure of p-benzoquinone-N,N?-bis-methylsulfonyldiimine

Cited by 2 publications

References 10 publications

Benzo-Bridged Bis(1,2,3-dithiazoles) and Their Selenium Analogues. Preparation, Molecular and Electronic Structures, and Redox Chemistry

Benzo-Bridged Bis(1,2,3-dithiazoles) and Their Selenium Analogues. Preparation, Molecular and Electronic Structures, and Redox Chemistry

Synthesis and Reactivity of a Cobalt-Supported Singlet Nitrene

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