Studies on electrochemical and coordination behaviour of phosphiniminocyclotrithiazenes

Swarnalatha, U; Sivaramakrishna, A; Venkatachalam, C S; Rao, MN Sudheendra; Inoue, Tomonori; Ueda, Tadaharu; Hojo, Masashi
November 2002
Canadian Journal of Chemistry;Nov2002, Vol. 80 Issue 11, p1428
Academic Journal
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.


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