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Synthesis and Study of Physico-Chemical Behaviour of Complexes Containing Heterometallic Trinuclear Triangular Metal-Sulfur-Cubiodal {WMo2S4}4+ Core
Corresponding Author(s) : Ramjee Sah
Asian Journal of Chemistry,
Vol. 25 No. 8 (2013): Vol 25 Issue 8
Abstract
Chromatographic separation of mixture leads to the isolation of molybdenum-tungsten mixed-metal clusters [MoW2S4(H2O)9]4+ and [WMo2S4(H2O)9]4+. From the aqua ion the corresponding oxalato-derivatives as [MoW2S4(C2O4)3(H2O)3]2- and [WMo2S4(C2O4)3(H2O)3]2- were isolated. The peak positions of the two big bands in each infrared spectrum of the four aqua clusters, [Mo3S4(H2O)9]4+, [W3S4(H2O)9]4+, [MoW2S4(H2O)9]4+ and [WMo2S4(H2O)9]4+ in the 550-400 cm-1 region shift to lower wave number when the molybdenum atom is replaced by tungsten. The cyclic voltammogramms of Cs2[MoW2S4(C2O4)3(H2O)3] (1) B and Cs2[WMo2S4(C2O4)3(H2O)3] (2) shows three consecutive one-electron reduction steps in the aqueous medium with supporting electrolyte, KCl at -0.84, -1.40, -1.78 and -0.73, -1.22, -1.66V respectively. These steps correspond to the change of oxidation states of three metals in each cluster with the following electronic configuration{M3}6 ® {M3}7®{M3}8 ®{M3}9. The half wave potential E1/2 are significantly dependent on the cluster metals. In all the reduction processes the [MonW3-nS4(C2O4)3(H2O)3]2- clusters (n = 0-3) are easily reduced with the increase in the number of Mo(n) in the clusters. The proceeding reduction centre of the molybdenum-tungsten mixed metal clusters is mainly on the Mo atom(s) rather than W atoms.
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References
(a) T. Shibahara, Coord. Chem. Rev., 123, 73 (1993); (b) T. Shibahara, Adv. Inorg. Chem., 37, 143 (1991).
(a) T. Shibahara, M. Yamasaki, G. Sakane, K. Minami, T. Yabuki and A. Rhimura, Inorg. Chem., 31, 640 (1992); (b) Q.- T. Liu, J.-X. Lu and A.G. Sykes, Inorg. Chim. Acta, 200, 623 (1992).
F.A. Cotton and S.K. Mandal, Inorg. Chim. Acta, 192, 71 (1992).
F.A. Cotton and W. Schwotzer, Angew. Chem., 94, 652 (1982).
M.H. Chisholer, K. Folting, J.C. Huffman and E.M. Kober, Inorg. Chem., 24, 241 (1985).
(a) B. Wang, Y. Sasaki, A. Nagasawa and T. Ito, J. Am. Chem. Soc., 108, 6059 (1986); (b) B. Wang, Y. Sasa ki, S. Ikari, K. Kimura and T. Ito, Chem. Lett., 1955 (1987).
A. Patel and D.T. Richers, J. Chem. Soc. Chem. Commun., 274 (1990).
H. Brunner, H. Kanermann and J. Wachter, J. Organomet. Chem., 265, 189 (1984).
(a) N.Y. Zhu, Y.-F. Zhing and X.-T. Wn, Inorg. Chem., 29, 2705 (1990); (b) N.-Y. Zhu, Y.-F.- Zhing and X.-T. Wu, Polyhedram, 10, 2743 (1991).
N.-Y, Zhu, Y.-F. Zheing and X.-T. Wu, J. Chem. Soc. Chem. Common, 235 (1991).
(a) T. Shibahara, M.Y. Saki, T. Watase and A. Ichimura, Inorg. Chem., 33, 292 (1994); (b) A. Mullier, V.P. Feddin, E. Dienmann, H. Bogge, E. Krickemeyer, D. Solter, A.M. Guuliani, R. Barbieri and P. Adler, Inorg. Chem., 33, 2243 (1994).