TITLE

Studies on electrochemical and coordination behaviour of phosphiniminocyclotrithiazenes

AUTHOR(S)
Swarnalatha, U; Sivaramakrishna, A; Venkatachalam, C S; Rao, MN Sudheendra; Inoue, Tomonori; Ueda, Tadaharu; Hojo, Masashi
PUB. DATE
November 2002
SOURCE
Canadian Journal of Chemistry;Nov2002, Vol. 80 Issue 11, p1428
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Electrochemical (polarographic, cyclic voltammetric, and coulometric) and coordination behaviour of several symmetrically and unsymmetrically substituted phosphiniminocyclotrithiazenes have been studied. Polarograms of R[sub 3] PN-S[sub 3] N[sub 3] (R = C[sub 6] H[sub 5] , p-ClC[sub 6] H[sub 4] , p-H[sub 3] CC[sub 6] H[sub 4] , and (OC[sub 4] H[sub 8] N)), Ph[sub 2] (OC[sub 4] H[sub 8] N)PN-S[sub 3] N[sub 3] , and Ph(OC[sub 4] H[sub 8] N)[sub 2] PN-S[sub 3] N[sub 3] give two cathodic waves. Cyclic voltammograms of Ph[sub 3] PN-S[sub 3] N[sub 3] (1) and (OC[sub 4] H[sub 8] N)[sub 3] PN-S[sub 3] N[sub 3] (2) reveal nearly the same oxidation peak potential but different reduction potentials. Controlled potential electrolysis of 1 and 2 at +0.6 V indicates exocyclic cleavage and ring degradation. Cathodic reduction behaviour of Ph[sub 3] PN-S[sub 3] N[sub 3] suggests the possibility for the formation of 1,5-(Ph[sub 3] PN)[sub 2] S[sub 4] N[sub 4] under electrochemical conditions. Reaction of nickel chloride hexahydrate with heterocycle 1 in 1:2 molar ratio in acetonitrile affords the complex, [Ni(S[sub 2] N[sub 2] H)[sub 2] ] (A) (90% yield) and [Ph[sub 3] PNH[sub 2] ]Cl salt as products. Analogous reactions with other ligands of this type (two symmetrical (sym.) and three unsymmetrical (unsym.)) except 2 also give A, while ligand 2 reacts with anhyd NiCl[sub 2] in an equimolar ratio to afford a dark green, square-planar complex ((OC[sub 4] H[sub 8] N)[sub 3] PN-S[sub 3] N·NiCl[sub 2] (B)) whose ESCA results assist in providing its coordination details. The study reveals a high tendency of these heterocycles to different types of ring cleavage. Key words: phosphiniminocyclotrithiazenes, polarography and cyclic voltammetry, substituent effect, nickel complexes, ESCA.On a étudié le comportement électrochimique (polarographique, voltampérométrie cyclique et coulométrique) et de coordination de plusieurs phosphiniminocyclotrithiazènes substitués de façon symétrique et asymétrique. Les polarogrammes des R[sub 3] PN-S[sub 3] N[sub 3] (R = C[sub 6] H[sub 5] , p-ClC[sub 6] H[sub 4] , p-H[sub 3] CC[sub 6] H[sub 4] , OC[sub 4] H[sub 8] N) Ph[sub 2] (OC[sub 4] H[sub 8] N)PN-S[sub 3] N[sub 3] et Ph(OC[sub 4] H[sub 8] N)[sub 2] PN-S[sub 3] N[sub 3] présentent deux vagues cathodiques. Les voltampérogrammes cycliques du Ph[sub 3] PN-S[sub 3] N[sub 3] (1) et (OC[sub 4] H[sub 8] N)[sub 3] PN-S[sub 3] N[sub 3] (2) présentent des potentiels d'oxydation maxima qui sont pratiquement les mêmes, mais les potentiels de réduction sont différents. Une électrolyse du composé 1 à potentiel contrôlé, à 0,6 V, indique la présence de clivage exocyclique et de dégradation de cycle. Le comportement du Ph[sub 3] PN-S[sub 3] N[sub 3] lors de la réduction cathodique suggère la possibilité de formation du 1,5-(Ph[sub 3] PN)[sub 2] S[sub 4] N[sub 4] dans les conditions électrochimiques. La réaction du chlorure de nickel hexahydraté avec l'hétérocycle 1, dans un rapport molaire de 2:1 dans l'acétonitrile, conduit à la formation du complexe [Ni(S[sub 2] N[sub 2] H)[sub 2] ] (A) (rendement de 90 %) et du [Ph[sub 3] PNH[sub 2] ]Cl. Des réactions analogues (excepté celles avec le produit 2) avec d'autres ligands de ce type (deux symétriques et trois non symétriques) conduisent aussi au produit à A. Le composé 2 réagit avec le NiCl[sub 2] anhydre, dans un rapport moléculaire de 1:1, pour fournir un complexe plan carré, vert, (OC[sub 4] H[sub 8] N)[sub 3] PN-S[sub 3] N·NiCl[sub 2] (B) dont les résultats de spectroscopie d'électrons pour analyse chimique (« ESCA ») fournissent des détails relatifs à sa coordination. Cette étude révèle la grande tendance de ces hétérocycles à donner lieu à des types différents de clivage de cycle. Mots clés : phosphiniminocyclotrithiazènes, polarographie, voltampérométrie cyclique, effet de substituant, complexes de nickel, ESCA.
ACCESSION #
10587592

 

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