Metal-Sulphur Aggregates and Clusters
Authors
-
Department of Chemistry, Jadavpur University, Calcutta 700 032 ,IN
Prasanta K. Chakrabarty -
Department of Chemistry, Jadavpur University, Calcutta 700 032 ,INProdip N. Ghosh
-
Department of Chemistry, Jadavpur University, Calcutta 700 032 ,INIndrtgit Ghosh
-
Department of Chemistry, Jadavpur University, Calcutta 700 032 ,INRamgopal Bhattacharyya
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.Downloads
Downloads
Published
How to Cite
Issue
Section
References
(a) F A Cotton, G Wilkinson, Advanced Inorganic Chemistry, 5th ed, John Wiley and Sons Inc, New York, 1988.
(b) E I Stiefel, Prog Inorg Chem, 22, 1, 1977.
(c) K B Swedo, J H Enemark, J Chem Educ, 56, 70, 1979.
(a) K B Krauskopf, Introduction to Geochemistry, McGraw Hill, New York, 1979.
(b) T R Halbert, R R Hutchings, E I Stiefel, J Am Chem Soc, 109, 6437, 1986
(c) A Muller, E Diemann, R Jostes, Naturwissenschaften, 71, 420, 1984.
I Yamamoto, T Saiki, S M Liu, L G Ljundhal, J Biol Chem, 258, 1826, 1983.
F S Delk, M J Sienko, Inorg Chem, 19, 1352, 1980 J D Corbett, J Solid State Chem, 39, 56, 1981.
M Rakowski DuBois, Chem Reviews, 89, I. 1989
A Bhattacharyya, J Bose, K Das, A B Chatterjee, R G Bhattacharyya, Rohatgi-K K Mukherjee, Hydrogen Energy Prog, 2, 771, 1982.
A Bhattacharjrya, J Bose, K Das, R G Bhattacharyya, A B Chatterjee, Rohatgi-K K Mukherjee, Bull Chem Soc Jpn, 56, 939, 1983.
R G Bhattacharyya, D P Mandal, Rohatgi-K K Mukherjee, Bull Mater Sci, 10, 373, 1988.
A Muller, E Diemann, R Jostes, H Bogge, Angew Chem Int Ed Engl, 20, 934
A Muller, Polyhedron, 5, 323.
MA Harmer, T R Halbert, W H Pan, C L Coyle, S A Cohen, and E I Stiefel, Polyhedron, 5, 341, 1986.
A Muller, E Diemann, Adv Inorg Cliem, 31, 89, 1987.
D Coucouvanis, A Toupadakis, S M Koo, A Hadijikyriacou, Polyhedron, 8, 1705.
X Q Xin, G X Jin, B Wang. N T Pope, Inorg Chem 29, 553, 1990.
T Shibahara, Coord Chem Reiv, 123, 73, 1993.
A MuUer, R G Bhattacharyya, Pfefferkorn, B Chem Ber, 112, 778, 1979.
R G Bhattacharyya, P K Chakrabarty, P N Ghosh, A K Mukherjee, D Podder, M Mukherjee, Inorg Chem, 30, 3948, 1991.
P K Chakrabarty, S Bhattacharyya, C G Pierpont, R G Bhattacharyya, Inorg Chem, 31, 3573, 1992.
R Steudel, in Sulfur, Its Significance for Chemistry, for the Geo-, Bio-, and Coemosphere and Technology,
A Muller and B Krcbs (Eds), Studies in Inorganic Chemistry, Volume 5, Elsevier Science Publishers, B V Amsterdam. «7-89, 1984.
S Licht, G Hodes, J Manassen, Inorg Chem, 25, 2486, 1986.
A Muller, J Schimanski, U Schimanski, H Bogge, Z Naturforch, 40b, 1277, 1985.
F Seel, in Sulfur, Its Significance for Chemistrj', for the Geo-, Bio- and Cosmosphere and Technology, A Muller and B Krebs, (Bis), Studies in Inorganic Chemistry, Volume 5, Elsevier Science Publishers, B V Amsterdam, 67-89, 1984.
M Draganjac, T B Rawchfuss, Angew Chem Ini Ed Engl, 24, 742, 1985.
H Funk, H Bohland, Z Anorg Allg Chen, 318, 169, 1962. R G Bhattacharyya, unpublished work.
F W Baumann, Diplom Arbeit (MS Thesis), University of Bielefeld, Bielefeld, FRG, 1994, W Eltzner, Ph D Dissertation, University of Bielefeld, Bielefeld, FRG, 1984.
F A Cotton, Reu Pure Appl Chem, 17, 25, 1967, Ace Chem Res, 2, 240, 1969.
(a) N C Howlader, G P Haight Jr, T W Hambley, M R Snow, G A Lawrance, Inorg Chem, 23, 1811, 1984.
(b) V R Ott, D S Sweiter, F A Schultz, Inorg Chem, 16, 2583, 197J.
(c) F A Schultz, V R Ott, D S Rolison, D C Bravard, J W Mcdonald, W E Newton, Inorg Chem, 17, 1758, 1978.
