Studies on π-acceptor molecules containing the dicyanomethylene group. X-Ray crystal structure of the charge-transfer complex of tetramethyltetrathiafulvalene and 2,3-dicyano-1,4-naphthoquinone: (TMTTF)3–(DCNQ)2

1993 ◽  
pp. 313-319 ◽  
Author(s):  
Andrei S. Batsanov ◽  
Martin R. Bryce ◽  
Stephen R. Davies ◽  
Judith A. K. Howard ◽  
Roger Whitehead ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Charge Transfer ◽  
Charge Transfer Complex ◽  
X Ray ◽  
Acceptor Molecules

scholarly journals Isolation and X-ray Crystal Structure of an Electrogenerated TEMPO–N3 Charge-Transfer Complex

2021 ◽  
Author(s):  
Hosea M. Nelson ◽  
Juno C. Siu ◽  
Ambarneil Saha ◽  
Duilio Cascio ◽  
Samantha N. MacMillan ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Charge Transfer ◽  
Charge Transfer Complex ◽  
X Ray

scholarly journals Isolation and X-ray Crystal Structure of an Electrogenerated TEMPO–N3 Charge-Transfer Complex

2020 ◽  
Author(s):  
Hosea Nelson ◽  
Juno Siu ◽  
Ambarniel Saha ◽  
Duilio Cascio ◽  
Song-Bai Wu ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Charge Transfer ◽  
Theoretical Analysis ◽  
Charge Transfer Complex ◽  
Reactive Intermediates ◽  
Structural Elucidation ◽  
Catalytic Reactions ◽  
X Ray ◽  
Increasing Demand ◽  
Computational Predictions

Recent advances in radical-based catalytic reactions have created an increasing demand for the understanding of their mechanistic underpinnings. Structural elucidation of transient reactive intermediates via diffraction techniques, though rarely possible, is one of the most decisive ways to support such mechanistic hypotheses. Here we present the isolation, structural elucidation, and theoretical analysis of an electrochemically generated and catalytically relevant charge-transfer species formed between the azidyl radical and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO). The unusual bent N–N–N angle and the pancake bonding between these two fragments highlight the weak bonding interactions present in this complex. This X-ray structure validates computational predictions as well as mechanistic proposals of TEMPO-mediated radical azidation reactions.

Photochemical Nitration by Tetranitromethane. XVII. The Regiochemistry of Adduct Formation in the Photochemical Reaction of 1-Methylnaphthalene and Tetranitromethane

1994 ◽  
Vol 47 (8) ◽  
pp. 1591 ◽  
Author(s):  
JL Calvert ◽  
L Eberson ◽  
MP Hartshorn ◽  
n Maclaga ◽  
WT Robinson
Keyword(s):  
Crystal Structure ◽  
Charge Transfer ◽  
Radical Cation ◽  
Photochemical Reaction ◽  
Charge Transfer Complex ◽  
Adduct Formation ◽  
X Ray ◽  
Analogous Manner ◽  
Structure Determinations ◽  
Ion Recombination

Photolysis of the 1-methylnaphthalene/tetranitromethane charge-transfer complex yields the triad of 1-methylnaphthalene radical cation, nitrogen dioxide and trinitromethanide ion. Recombination of this triad gives predominantly 4-methyl-t-2-nitro-r-1-trinitromethyl-1,2- dihydronaphthalene (1), the epimeric 1-methyl-1-nitro-4-trinitromethyl-1,4-dihydronaphtha-lenes (2) and (3), 8-methyl-c-4-trinitromethyl-1,4-dihydronaphthalen-r-l-ol (4), nitro cyclo -adduct (5), 8-methyl-c-4-trinitromethyl-1,4-dihydronaphthalen-r-l-ol (6), hydroxy cyclo-adduct (7) and 4-methyl-t-1-trinitromethyl-1,2-dihydronaphthalen-r-2-ol (8). Adducts (1)- (3), (5), (7) and (8) are formed by attack of the trinitromethanide ion at C4 of the 1-methylnaphthalene radical cation, while adducts (4) and (6) are formed by corresponding attack at C5. Adduct (1) undergoes thermal cycloaddition to give the nitro cycloadduct (5) and it is assumed that the hydroxy cycloadduct (7) is formed in analogous manner from 4-methyl-t-1-trinitromethyl-1,2-dihydronaphthalen-r-2-ol (8). X-Ray crystal structure determinations are reported for adducts (1), (3)-(5) and (7).

Photochemical Nitration by Tetranitromethane. XXXII. Adduct Formation in the Photochemical Reaction of Phenanthrene and Tetranitromethane

1996 ◽  
Vol 49 (4) ◽  
pp. 469
Author(s):  
CP Butts ◽  
L Eberson ◽  
KL Fulton ◽  
MP Hartshorn ◽  
WT Robinson
Keyword(s):  
Crystal Structure ◽  
Charge Transfer ◽  
Nitrogen Dioxide ◽  
Photochemical Reaction ◽  
Charge Transfer Complex ◽  
Major Product ◽  
Adduct Formation ◽  
X Ray ◽  
Structure Determinations ◽  
Ion Recombination

Photolysis of the phenanthrene/tetranitromethane charge-transfer complex yields the triad of phenanthrene radical cation, nitrogen dioxide, and trinitromethanide ion. Recombination of this triad in dichloromethane at 20° gives 9-nitrophenanthrene (1), trans-10-trinitromethyl-9,10-dihydrophenanthren-9-yl nitrate (2a), trans-9-nitro-10-trinitromethyl-9,10-dihydrophenanthrene (2b), and trans-10-trinitromethyl-9,10-dihydrophenanthren-9-ol (2c). Adduct formation is partially suppressed when trifluoroacetic acid (0.7 M) is added to the dichloromethane solvent at 20°, the major product identified being 9-nitrophenanthrene (1). At -20° in dichloromethane, or in acetonitrile at 20°, 10'-nitro-9,9',10,10'-tetrahydro-9,9'-biphenanthren-10-yl nitrate (3) is formed, apparently by reaction of nitrogen dioxide with phenanthrene. X-Ray crystal structure determinations are reported for adducts (2a,b).

Electrochromism and X-ray Crystal Structure of a Mixed-Valence Charge-Transfer Complex [(CH3)2NC6H4NH(CH3)2]4[(C4H9)4N]SiMo12O40

1997 ◽  
Vol 9 (12) ◽  
pp. 2687-2689 ◽  
Author(s):  
Xiao-Min Zhang ◽  
Bao-Zhen Shan ◽  
Zhi-Ping Bai ◽  
Xiao-Zeng You ◽  
Chun-Ying Duan
Keyword(s):  
Crystal Structure ◽  
Charge Transfer ◽  
Charge Transfer Complex ◽  
Mixed Valence ◽  
X Ray

scholarly journals Intermolecular interactions and charge transfer in the 2:1 tetrathiafulvalene bromanil complex, (TTF)2-BA

2011 ◽  
Vol 67 (3) ◽  
pp. 244-249 ◽  
Author(s):  
Pilar García-Orduña ◽  
Slimane Dahaoui ◽  
Claude Lecomte
Keyword(s):  
Crystal Structure ◽  
Phase Transition ◽  
Charge Transfer ◽  
Room Temperature ◽  
Charge Transfer Complex ◽  
Structural Phase ◽  
X Ray Diffraction ◽  
X Ray ◽  
Donor And Acceptor ◽  
A Charge

The crystal structure of the 2:1 charge-transfer complex of tetrathiafulvalene [2,2′-bis(1,3-dithiolylidene)] and bromanil (tetrabromo-1,4-benzoquinone) [(TTF)2-BA, (C6H4S4)2–C6Br4O2] has been determined by X-ray diffraction at room temperature, 100 and 25 K. No structural phase transition occurs in the temperature range studied. The crystal is made of TTF–BA–TTF sandwich trimers. A charge-transfer estimation between donor and acceptor (0.2 e) molecules is proposed in comparison to the molecular geometries of TTF–BA and TTF and BA isolated molecules. Displacement parameters of the molecules have been modeled with the TLS formalism.

scholarly journals Isolation and X-ray Crystal Structure of an Electrogenerated TEMPO–N3 Charge-Transfer Complex

2020 ◽  
Author(s):  
Hosea Nelson ◽  
Juno Siu ◽  
Ambarniel Saha ◽  
Duilio Cascio ◽  
Song-Bai Wu ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Charge Transfer ◽  
Theoretical Analysis ◽  
Charge Transfer Complex ◽  
Reactive Intermediates ◽  
Structural Elucidation ◽  
Catalytic Reactions ◽  
X Ray ◽  
Increasing Demand ◽  
Computational Predictions

Recent advances in radical-based catalytic reactions have created an increasing demand for the understanding of their mechanistic underpinnings. Structural elucidation of transient reactive intermediates via diffraction techniques, though rarely possible, is one of the most decisive ways to support such mechanistic hypotheses. Here we present the isolation, structural elucidation, and theoretical analysis of an electrochemically generated and catalytically relevant charge-transfer species formed between the azidyl radical and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO). The unusual bent N–N–N angle and the pancake bonding between these two fragments highlight the weak bonding interactions present in this complex. This X-ray structure validates computational predictions as well as mechanistic proposals of TEMPO-mediated radical azidation reactions.

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