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Metal-Sulphur Aggregates and Clusters


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1 Department of Chemistry, Jadavpur University, Calcutta 700 032, India
     

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A Brief general account on dioxygen, disulphur, polysulphur and polysulphides has been furnished. It has been shown that while MoO42- on prolonged heating with aqueous polyaulphide ions (sx2-) furnishes a triangular and a binuclear Mo-S clusters, viz, [Mo3S(S2)6]2- and [Mo2(S2)6)2- respectively, a brief cooking affords (Mo2O2S2)2- moiety in the form of the complex [Mo2O2S2(S2)(S4)]2-. WO42- needs to be reduced to Wo3+ first and then furnished the complexes [W2O2S2(S2)(S4)]2- or [W2O2S2(S4)2]2-, but not the molybdenum analogues of the all-sulphur triangular or binuclear clusters. The solution containing (M2O2S2)2- (M=Mo, W) moiety and excess polysulphides when stirred with L-L ligands (bipy or phen) affords a red or orange-red solid wherefrom a binuclear complex [M2O2S2(NCS)2 (L-L2)]and a mononuclear product (MO(S2)2 (L-L)l are crystallised and structurally characterised. (Mo2O2S2)2+ core containing η2-S2 and η2-S4 in DMF undergoes reversible cyclic voltametric responses showing stepvrise reduction of two Mo(V) centres to Mo(IV). In the case of (W2O2S2)2+, the reduction is essentially a two electron single step process, the reverse sweep exhibiting two step single electron oxidative responses. The [W0(S2)2(L-L)) shows nearly reversible two step one electron reduction at the metal centre but the Mo-analogue shows irreversible electrochemical responses.
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  • Metal-Sulphur Aggregates and Clusters

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Authors

Prasanta K. Chakrabarty
Department of Chemistry, Jadavpur University, Calcutta 700 032, India
Prodip N. Ghosh
Department of Chemistry, Jadavpur University, Calcutta 700 032, India
Indrtgit Ghosh
Department of Chemistry, Jadavpur University, Calcutta 700 032, India
Ramgopal Bhattacharyya
Department of Chemistry, Jadavpur University, Calcutta 700 032, India

Abstract


A Brief general account on dioxygen, disulphur, polysulphur and polysulphides has been furnished. It has been shown that while MoO42- on prolonged heating with aqueous polyaulphide ions (sx2-) furnishes a triangular and a binuclear Mo-S clusters, viz, [Mo3S(S2)6]2- and [Mo2(S2)6)2- respectively, a brief cooking affords (Mo2O2S2)2- moiety in the form of the complex [Mo2O2S2(S2)(S4)]2-. WO42- needs to be reduced to Wo3+ first and then furnished the complexes [W2O2S2(S2)(S4)]2- or [W2O2S2(S4)2]2-, but not the molybdenum analogues of the all-sulphur triangular or binuclear clusters. The solution containing (M2O2S2)2- (M=Mo, W) moiety and excess polysulphides when stirred with L-L ligands (bipy or phen) affords a red or orange-red solid wherefrom a binuclear complex [M2O2S2(NCS)2 (L-L2)]and a mononuclear product (MO(S2)2 (L-L)l are crystallised and structurally characterised. (Mo2O2S2)2+ core containing η2-S2 and η2-S4 in DMF undergoes reversible cyclic voltametric responses showing stepvrise reduction of two Mo(V) centres to Mo(IV). In the case of (W2O2S2)2+, the reduction is essentially a two electron single step process, the reverse sweep exhibiting two step single electron oxidative responses. The [W0(S2)2(L-L)) shows nearly reversible two step one electron reduction at the metal centre but the Mo-analogue shows irreversible electrochemical responses.

References