<b>Chemistry of Tetracyanoethylene Anion Radical</b>

Webster, Owen W.; Mahler, Walter; Benson, R. E.

doi:10.1021/ja00878a017

Cited by 189 publications

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“…Fax: 54-58-680280. E-mail: nitas@unrccc.edu.ar iodide ion complete electron transfer occurs and the stable TCNE anion is formed (2). The acceptor properties of TCNE as well as its multiple applications in organic chemistry have been comprehensively reviewed (3).…”

Section: Ma Biasutti and Jj ~Ilber' Departamento De Quimica Ymentioning

confidence: 99%

Interaction between tetracyanoethylene and naphthalene in reverse micelles of AOT in n-hexane. The electron-donor properties of AOT

Biasutti¹,

Silber²

1996

Can. J. Chem.

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Abstract:The electron donor-acceptor (EDA) interaction between TCNE and naphthalene (Naph) in rz-hexane and reverse micelles of AOT in n-hexane was studied by UV-visible spectroscopy with the aim of determining the influence of the micellar media on the EDA interaction. The spectra of the mixtures of TCNE-Naph in 11-hexane show two typical maxima at 418 and 534 nm, assigned to the formation of a T-IT EDA complex. In the micellar media a new band is observed at 398 nm. When the spectra of TCNE in 11-hexane are studied in the presence of AOT two new bands at 398 and 4 18 nm are detected. These bands are consistent with an EDA interaction between TCNE and AOT as 11-donor. The stability constants of this interaction were calculated for AOT concentrations below the CMC and in the micellar media at differentThe results give evidence of the tendency of AOT to interact very strongly with electron acceptors. Moreover, in the system TCNE-Naph in the micellar media it is shown that Naph and AOT compete to form a complex with TCNE. The formation constants of the complexes of AOT-Naph in the micelle system were determined at W = 0 and 5. Despite the competition of AOT for TCNE the stability constant for the complex TCNE-Naph is higher than in homogeneous media, probably due to the high local concentration of the acceptor in the micelle.Key rvords : reverse micelles, aerosol-OT, tetracyanoethylene, naphthalene, electron donor-acceptor complexes. De plus, on a montrC que, dans le systkme TCNE-Naph en milieu micellaire, Naph et AOT sont en competition pour former un complexe avec TCNE. On a determink les constantes de formation des complexes AOT-Naph W = 0 et 5. MalgrC la compCtition de AOT pour TCNE, la constante de stabilitC pour le complexe TCNE-Naph est plus ClevCe dans le milieu homogkne, probablement en raison de la concentration locale plus ClevCe de I'accepteur dans la micelle.

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Section: Ma Biasutti and Jj ~Ilber' Departamento De Quimica Ymentioning

confidence: 99%

Interaction between tetracyanoethylene and naphthalene in reverse micelles of AOT in n-hexane. The electron-donor properties of AOT

Biasutti¹,

Silber²

1996

Can. J. Chem.

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“…TCNE ion radical was surprisingly stable, and we did not find much excitement in its chemistry. 5 It did, however, lead to several new nuggets on our discovery trail. Its electron spin resonance (ESR) spectrum showed up as a rock-stable nine-line pattern used for many years by our ESR lab as a standard.…”

Section: Methodsmentioning

confidence: 99%

“…Its electron spin resonance (ESR) spectrum showed up as a rock-stable nine-line pattern used for many years by our ESR lab as a standard. 5,6 In a sealed tube the ion radical lasted indefinitely, but in air the signal quickly dissipated as a result of a reaction with oxygen and water.…”

Section: Methodsmentioning

confidence: 99%

“…TCNE with a half-wave potential of 0.15 V versus standard calomel electrode (SCE) is easily reduced by potassium iodide. 5 However, the most unusual reducing agent is cyanide. 5 A mechanism study of this system showed that cyanide was adding to TCNE to give pentacyanoethanide (13) that reacted with more cyanide to give tetracyanoethandiide (14) and cyanogen.…”

Section: Methodsmentioning

confidence: 99%

“…5 However, the most unusual reducing agent is cyanide. 5 A mechanism study of this system showed that cyanide was adding to TCNE to give pentacyanoethanide (13) that reacted with more cyanide to give tetracyanoethandiide (14) and cyanogen. The diide quickly transfers an elec-tron to TCNE to give two molecules of ion radical.…”

Section: Methodsmentioning

confidence: 99%

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Cyanocarbons: A classic example of discovery‐driven research

Webster

2001

J. Polym. Sci. A Polym. Chem.

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ABSTRACT:Cyanocarbons are organic compounds bearing enough cyano functional groups to significantly alter their chemical properties. For example, tetracyanoethylene forms a stable anion radical, is a strong acid, and readily substitutes its cyano groups. Tetracyanoethylene oxide reacts by addition across its carbon-carbon bond. Diazodicyanoimidazole cleaves nitrogen to form a superelectrophilic carbene, and pentacyanocyclopentadiene is about as acidic as perchloric acid. In this highlight, discovery-driven research that fanned out from tetracyanoethylene to a multiperson effort at DuPont on cyanocarbon chemistry is narrated.

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Synthesis and Reactivity of the TlI salts of [TCNE].− and [TCNE]2−: The Structural Determination of TlI[TCNE] and [TDAE][TCNE]2 and Evidence for a Chelated [TCNE].−

et al. 2000

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Synthons Tl1[TCNE]*- (1) and Tl12[TCNE]2- (2), for [TCNE]*- and [TCNE]2-, respectively, in metathesis reactions have been quantitatively prepared and characterized. The structure of 1 was solved and refined in a monoclinic unit cell at 27 degrees C [C2/c, a = 12.6966 (12) angstroms, b=7.7599 (7) angstroms, c=15.5041 (15) angstroms, beta = 96.610 (5) degrees , V= 1517.4 (2) angstroms3, Dcalcd = 2.911 gcm-3, Z=8, R1 = 0.0575, omegaR2=0.0701] and exhibits nuCN absorptions at 2,191 (s) and 2,162 (s) cm-1 consistent with metal-bound [TCNE]*-. The structure of 1 consists of a distorted square antiprismatic octacoordinate Tl1 bound to six monodentate [TCNE]*-s with TlN separations ranging from 2.901 to 3.171 angstroms averaging 3.020 angstroms, and one bidentate [TCNE]*- with TlN separations averaging 3.279 angstroms. The TlN bonding is attributed to electrostatic bonding. The [TCNE]*-s form dimerized zigzag chains with intra- and interdimer separations of 2.87 and 3.29 angstroms, respectively. The tight pi-[TCNE](2)2- dimer is diamagnetic and has the shortest intradimer [TCNE]*- distance reported. These synthons for [TCNE]*- and [TCNE]2- in metathesis reactions lead to the precipitation of, for example, TlIX (X = Cl, Br, OAc). Reaction of 1 with MnIII(porphyrin)X (X = Cl, OAc) forms the molecule-based magnets of [MnIII(porphyrin)][TCNE] composition, while the reaction of [CrI(C6H6)2]Br and (Me2N)2CC(NMe2)2Cl2, [TDAE]Cl2, with 1 forms [CrI(C6H6)2] [TCNE] and [TDAE][TCNE]2, respectively. The structure of [TDAE][TCNE]2.MeCN was solved and refined in an orthorhombic unit cell at 21 degrees C [I222, a = 10.2332(15), b = 13.341(6), c = 19.907(8) angstroms, V= 2717.7 angstroms3, Z = 4; Dcalcd = 1.216 gcm-3, R=0.083, Romega = 0.104] and exhibits upsilonCN absorptions at 2,193 (m), 2,174 (s), and 2,163 (s) cm-1 consistent with isolated [TCNE](2)2- , in contrast to the aforementioned TlI bound [TCNE](2)2-. The reaction of 2 with [TDAE]Cl2 forms [TDAE]2+[TCNE]2-.

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Chemistry of Tetracyanoethylene Anion Radical

Cited by 189 publications

References 0 publications

Interaction between tetracyanoethylene and naphthalene in reverse micelles of AOT in n-hexane. The electron-donor properties of AOT

Interaction between tetracyanoethylene and naphthalene in reverse micelles of AOT in n-hexane. The electron-donor properties of AOT

Cyanocarbons: A classic example of discovery‐driven research

Synthesis and Reactivity of the TlI salts of [TCNE].− and [TCNE]2−: The Structural Determination of TlI[TCNE] and [TDAE][TCNE]2 and Evidence for a Chelated [TCNE].−

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