Electrochemical synthesis of poly(sulphur nitride)

Banister, Arthur J.; Hauptman, Z.; Kendrick, A. G.

doi:10.1039/c39830001016

Cited by 14 publications

(3 citation statements)

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“…so,c1-. Cyclic Voltammetric Studies of the S,N,+ Ion.-Further to our report of the electrochemical reduction of [S,N,]Cl to (SN), in liquid SO,, 7 we investigated the mechanism of reaction using cyclic voltammetry. The results indicated that direct electrocrystallization might be achieved by electroreduction of [S,N,][BF,] in acetonitrile using a platinum or (SN),-coated cathode; the mechanism of this reaction was also studied using cyclic voltammetry.…”

Section: Resultsmentioning

confidence: 99%

Some investigations of S5N5 + compounds; X-ray crystal structure of [S5N5]Cl

Banister¹,

Hauptman²,

Kendrick³

et al. 1987

J. Chem. Soc., Dalton Trans.

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Aluminium chloride is removed from cyclopenta (azathienium) tetrachloroaluminate by tetrahydrofuran t o give pure [S,N,]CI and this reacts with aqueous tetrafluoroboric acid t o give [S,N,] [ BF,]. Cyclic voltammograms of [S,N,] CI in liquid SO, show reduction of S , N : at € ; $ = 0.34 V vs. a saturated calomel electrode; the process is reversible. Cyclic voltammograms of [S,N,] [BF,] in MeCN were more complex and a mechanism for this electroreduction is proposed. Electrodeposition of (SN)x o n platinum-foil and on (SN)x-film cathodes was achieved by potentiostatic electrolysis. [S,N,] CI crystallizes in the monoclinic space group C2/c, with a = 7.98(1), b = 14.37(1), c = 7.30(1) A, p = 97.15(5)", and Z = 4. 1 366 Observed reflections were refined t o R = 0.054. The mean bond angles are NSN 1 1 1.3 and SNS 140.2". Three of the five unique S-N distances are 158.2 pm but t w o [S(2)-N(2) 156.5, S(3)-N(3) 159.8 pm] are affected by short S . -. CI contacts [3.277(1) and 3.1 48(1) A at S(2) and 3.243(1) and 3.279(1) A at S(3)]. Strain in the azulene-shaped cation arising from cation-anion interactions can be detected by comparing bond distances and angles with the strain-free values deduced from either bond distance-bond angle correlation functions or M N DO calculations.The monocyclic cation SSNS+ is the 14-2 member of the Huckel set of cyclothiazenes. Most reported salts contain large counter ions [e.g. S3N306,' SnCl,(OPC13)-,2 A1C14-,3 GaC14-,4 Ga,Cl,-' 1 and, with colourless anions, the salts are yellow. The chloride, however, is red indicating either significant cation-anion interaction and/or a different cation conformation. Two isomers of SSNS+ have been reported from X-ray structure determinations (with an azulene 1*2*4 or 'heart' shape ,v4).The apparent heart shape may well arise from cation size di~order,~ but since MNDO calculations show that the two shapes probably have similar energy, genuine isomerism is still possible. We have therefore determined the structure of SSNS+CI-and find significant cation-anion interaction associated with the reentrant portion of an azulene-type SSNS+ ring. We also report a new preparation of [S,N,]CI from [S,N,][AICl,] and tetrahydrofuran (thf) and describe a solvate, We have investigated further the electrochemical reduction of SSNS+ (S,N,+Cl--SO,, S,N,+BF~-LiClO,-MeCN) to the conducting polymer (SN),, on both a macro-and microelectrode scale. In a broader context, the purpose of this investigation was (i) to elucidate the reaction mechanism at the electrode surfaces under various conditions, (ii) to work out a preparation method for pure polycrystalline (SN), (in quantities of tenths of a gram per batch) suitable as a source for vacuum deposition of electrically conductive films, and (iii) to explore the possibility of a direct electrochemical coating with compact layers of (SN), (lo2-lo4 A thick) on conducting or semi-conducting substrates.[SSN,]Cl*SO,.t Cyclopenta(azathienium) chloride.

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Section: Resultsmentioning

confidence: 99%

Some investigations of S5N5 + compounds; X-ray crystal structure of [S5N5]Cl

Banister¹,

Hauptman²,

Kendrick³

et al. 1987

J. Chem. Soc., Dalton Trans.

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“…The reflectance spectrum of a film of electrochemical (SN) x is identical to that of (SN) x prepared from S 2 N 2 and differential scanning calorimetry suggests a higher degree of order and longer chains in electrochemical (SN) x when compared with the polymer prepared from (NSCl) 3 ±Me 3 SiN 3 . [14] Electrochemical reduction of [S 5 N 5 ][FeCl 4 ] on platinum electrodes in dichloromethane also yields (SN) x . [15] Other preparations, given to illustrate the range of reactions that can lead to (SN) x , are summarized in Table 1.…”

Section: Synthesismentioning

confidence: 99%

Poly(sulfur nitride): The First Polymeric Metal

Banister¹,

Gorrell

1998

Adv. Mater.

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“…87,88 Na 2 E 4 (prepared by stirring the appropriate quantities of sodium and elemental S/Se/Te together in liquid ammonia) was stirred together with M(CO) 6 (M = Mo, W) in DMF. The contrasting reactivity of S and Se versus Te is immediately apparent from equations(40)and(41).…”

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confidence: 99%