Electrochemical studies of some dithiadiazolylium cations; evidence for the dithiadiazolide anion, [PhCNSSN]?

Aherne, Christine M.; Banister, Arthur J.; Gorrell, Ian B.; Hansford, Michael I.; Hauptman, Z.; Luke, Anthony W.; Rawson, Jeremy M.

doi:10.1039/dt9930000967

Cited by 40 publications

(24 citation statements)

References 9 publications

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“…The presence of the dithiadiazolyl ring was further confirmed by electrochemical studies; electrochemical studies on 4 • at room temperature in dichloromethane showed a reversible one-electron oxidation to the corresponding dithiadiazolylium cation [ ferrocene-ferrocenium couple), which is comparable to other reported reduction potentials for related CNSSN ring systems. [20] Solution and frozen solution EPR spectroscopy…”

Section: Resultsmentioning

confidence: 99%

EPR studies of the dynamics and phase behaviour of dithiadiazolyl radicals derived from mesogenic precursors

Rawson

Clarke

Bruce

2008

Magnetic Reson in Chemistry

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A series of liquid-crystalline materials based on 4-substituted cyanobiphenyls, RC(6)H(4)C(6)H(4)CN (R = C(5)H(11), C(6)H(13), C(7)H(15), C(8)H(17) and C(12)H(25), commonly referred to as 5CB, 6CB, 7CB, 8CB and 12CB, respectively) were functionalised to give the corresponding dithiadiazolyl organic radicals RC(6)H(4)C(6)H(4)CNSSN(*) (compounds 1(*), 2(*), 3(*), 4(*) and 5(*), respectively). EPR spectra of n-C(12)H(25)C(6)H(4)C(6)H(4)CNSSN(*) (5(*)) reveal that it adopts a dimeric diamagnetic structure in the solid state with a small number of paramagnetic defect sites. Variable temperature electron paramagnetic resonance (EPR) studies reveal a thermally activated rotation about the molecular long axis at temperatures above 314 K. The energy barrier to rotation about the phenylene-dithiadiazolyl bond was estimated as 25 kJ mol(-1) using density functional theory (DFT). At elevated temperatures thermal annealing was also observed, quenching the sample's paramagnetism.

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Section: Resultsmentioning

confidence: 99%

EPR studies of the dynamics and phase behaviour of dithiadiazolyl radicals derived from mesogenic precursors

Rawson

Clarke

Bruce

2008

Magnetic Reson in Chemistry

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“…The salts [p-BrC 6 H 4 CNSSN]Cl and [p-O 2 NC 6 H 4 CNSSN]Cl were prepared according to the literature method (17). Ph 3 Sb (Aldrich) was sublimed prior to use.…”

Section: Methodsmentioning

confidence: 99%

“…The two dithiadiazolylium salts, [p-BrC 6 H 4 CNSSN]Cl and [p-O 2 NC 6 H 4 CNSSN]Cl, were prepared according to the literature method (17). Oxidation of equimolar quantities of these two salts with dry O 2 according to the literature method yielded a mixture of the symmetric dithiatetrazocines, 1 and 2, as well as the unsymmetric derivative, 3.…”

Section: Preparation and Crystal Growthmentioning

confidence: 99%

Structural studies of dithiatetrazocines: X-ray crystal structures of the symmetric dithiatetrazocines p-XC₆H₄CN₄S₂CC₆H₄X [X = NO₂, Br] and the first unsymmetric dithiatetrazocine, p-BrC₆H₄CN₄S₂CC₆H₄NO₂

Bond¹,

Haynes²,

Rawson³

2002

Can. J. Chem.

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3). The structures of compounds 1-3 are determined by X-ray diffraction: 1 crystallizes in the monoclinic space group P2 1 /c (a = 8.6397(4), b = 5.8359(4), c = 14.9767(11) Å, b = 92.088(4)°) with half a molecule in the asymmetric unit; 2 crystallizes in the triclinic space group P1 (a = 6.5330(5), b = 8.2084 (6), c = 14.7264(9) Å, a = 84.483(4)°, b = 77.112(4)°, g = 87.879(3)°); 3 was found to crystallize in two forms: recrystallization from CH 2 Cl 2 at room temperature yielded a solvent-free, triclinic phase, space group P1 (a = 6.5060(9), b = 7.0739(9), c = 9.1164(8) Å, a = 81.860(3)°, b = 83.406(5)°, g = 66.589(5)°), whereas cooling a solution to -5°C yielded a solvated form, 3·CH 2 Cl 2 , which crystallizes in the monoclinic space group P2 1 /m (a = 6.179(1), b = 10.960(2), c = 13.884(3) Å, b = 92.69(3)°). The NO 2 ···Br intermolecular interactions observed in the unsolvated structure of 3 are disrupted in the solvate structure; the CH 2 Cl 2 molecule in the latter is aligned such that its molecular dipole interacts with both nitro and bromo groups, retaining a molecular chain motif. The structures are discussed in relation to their semi-empirically calculated molecular electrostatic potentials and calculations of intermolecular interactions using van der Waals forces combined with an electrostatic point charge model. Résumé: L'oxydation de quantités équimolaires de [p-BrC 6 H 4 CNSSN]Cl et de [p-O 2 NC 6 H 4 CNSSN]Cl avec de l'oxygène élémentaire, en présence de Ph 3 Sb, dans du MeCN, conduit à un mélange de dithiatétrazocines symétriques, O 2 NC 6 H 4 CN 4 S 2 CC 6 H 4 NO 2 (1) et BrC 6 H 4 CN 4 S 2 CC 6 H 4 Br (2), aux côtés du dérivé substitué de façon non symétrique, BrC 6 H 4 CN 4 S 2 CC 6 H 4 NO 2 (3). On a déterminé les structures des composés 1-3 par diffraction des rayons X: le composé 1 cristallise dans le groupe d'espace monoclinique P2 1 /c (a = 8,6397(4), b = 5,8359(4) et c = 14,9767(11) Å, b = 92,088(4)°), avec une demi-molécule dans la maille asymétrique; 2 cristallise dans le groupe d'espace triclinique P1 (a = 6,5330(5), b = 8,2084(6) et c = 14,7264(9) Å, a = 84,483(4)°, b = 77,112(4)°et g = 87,879(3)°); on a trouvé que 3 cristallise sous deux formes, la recristallisation dans le CH 2 Cl 2 , à température ambiante, conduit à des cristaux ne contenant pas de solvant, de phase triclinique et de groupe d'espace P1 (a = 6,5060(9), b = 7,0739(9) et c = 9,1164(8) Å, a = 81,860(3)°, b = 83,406(5)°et g = 66,589(5)°) alors que le refroidissement de la solution à -5°C livre une forme solvatée, 3·CH 2 Cl 2 qui cristallise dans le groupe d'espace monoclinique P2 1 /m (a = 6,179(1), b = 10,960(2) et c = 13,884(3) Å, b = 92,69(3)°). Les interactions intermoléculaires NO 2 ···Br observées dans la structure non solvatée de 3 sont interrompues dans la structure solvatée; la molécule de CH 2 Cl 2 de cette dernière est alignée d'une façon telle que son dipôle moléculaire interagit à la fois avec le groupe nitro et le bromo tout en maintenant un motif de chaîne moléculaire. On discute des structures en foncti...

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“…202-204 • C (decomposes). [21] 16.07%. 31 P-Nuclear magnetic resonance (NMR) spectroscopy of the remaining solution showed peaks at 23.9, 15.1, and 7.7 ppm, indicating the presence of Ph 3 P N S 3 N 3 , [Ph 2 PS 2 N 2 ] + Cl − , and Ph 4 P 2 N 3 SCl.…”

Section: With S 3 N 3 CL 3 1:1 C 6 H 6 -Ch 3 Cn Room Temperaturementioning

confidence: 98%

Single-Crystal X-Ray Structure and Reactivity of a Triphenylphosphinazine, (C₆H₅)₃P˭N‒N˭C(H)(C₆H₄NO₂-p)

Senthivel

Janaswamy

Gopalakrishnan

et al. 2011

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-

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Phosphinazines with "PNNC" framework comprise a novel class of compounds owing to the presence of both phosphinimino and ketimino moieties. There are very few known examples in this set and their utility toward exploring the chemistry is little known. We have embarked on a systematic investigation on this important class of compounds for delineating their coordination behaviour. Here we report the X-ray structure of free phosphinazine and its intrinsic functionality as a synthon to inorganic heterocycles and ligand in coordination chemistry. The p-nitrobenzaldehyde triphenylphosphoranylidenehydrazone (C 6 H 5 ) 3 P N N C(H)(C 6 H 4 NO 2 -p) molecules are arranged in a monoclinic lattice having P2 1 /n spatial arrangement with unit cell dimensions a = 8.7574(14) Å, b = 15.610(2) Å, c = 16.6566(12) Å, β = 104.828(8) • , and Z = 4. The analysis reveals trans orientation for the P N and C N moieties in the PNNC fragment. Extensive π conjugation starting from one of the phenyl rings on phosphorus to the p-nitrophenyl ring on carbon stabilizes the entire strip of the molecule. The reactions with S 4 N 4 , S 3 N 3 Cl 3 , and S 3 N 2 Cl 2 gave rise to the formation of six-membered cyclotrithiazene and other five-membered inorganic heterocycles. The coordination reactions with Mo(CO) 6 in the ratios 1:1 and 2:1 led to the formation of [Mo(CO) 5 L] and trans-[Mo(CO) 4 L 2 ], where L is the title phosphinazine.

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Electrochemical studies of some dithiadiazolylium cations; evidence for the dithiadiazolide anion, [PhCNSSN]?

Cited by 40 publications

References 9 publications

EPR studies of the dynamics and phase behaviour of dithiadiazolyl radicals derived from mesogenic precursors

EPR studies of the dynamics and phase behaviour of dithiadiazolyl radicals derived from mesogenic precursors

Structural studies of dithiatetrazocines: X-ray crystal structures of the symmetric dithiatetrazocines p-XC₆H₄CN₄S₂CC₆H₄X [X = NO₂, Br] and the first unsymmetric dithiatetrazocine, p-BrC₆H₄CN₄S₂CC₆H₄NO₂

Single-Crystal X-Ray Structure and Reactivity of a Triphenylphosphinazine, (C₆H₅)₃P˭N‒N˭C(H)(C₆H₄NO₂-p)

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Electrochemical studies of some dithiadiazolylium cations; evidence for the dithiadiazolide anion, [PhCNSSN]?

Cited by 40 publications

References 9 publications

EPR studies of the dynamics and phase behaviour of dithiadiazolyl radicals derived from mesogenic precursors

EPR studies of the dynamics and phase behaviour of dithiadiazolyl radicals derived from mesogenic precursors

Structural studies of dithiatetrazocines: X-ray crystal structures of the symmetric dithiatetrazocines p-XC6H4CN4S2CC6H4X [X = NO2, Br] and the first unsymmetric dithiatetrazocine, p-BrC6H4CN4S2CC6H4NO2

Single-Crystal X-Ray Structure and Reactivity of a Triphenylphosphinazine, (C6H5)3P˭N‒N˭C(H)(C6H4NO2-p)

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Structural studies of dithiatetrazocines: X-ray crystal structures of the symmetric dithiatetrazocines p-XC₆H₄CN₄S₂CC₆H₄X [X = NO₂, Br] and the first unsymmetric dithiatetrazocine, p-BrC₆H₄CN₄S₂CC₆H₄NO₂

Single-Crystal X-Ray Structure and Reactivity of a Triphenylphosphinazine, (C₆H₅)₃P˭N‒N˭C(H)(C₆H₄NO₂-p)