K8[Mo4S4(CN)12]&middot;4H2O: A New Alternative Synthetic Route for its Formation by Core Conversion from Trimer to Tetramer

Ramjee Sah; Balramjee Sah

doi:10.14233/ajchem.2013.14026

Issue

Vol. 25 No. 8 (2013): Vol 25 Issue 8

Issue Published : March 7, 2013

This work is licensed under a Creative Commons Attribution 4.0 International License.

K8[Mo4S4(CN)12]·4H2O: A New Alternative Synthetic Route for its Formation by Core Conversion from Trimer to Tetramer

https://doi.org/10.14233/ajchem.2013.14026

Ramjee Sah

University Department of Chemistry, B.R.A. Bihar University, Muzaffarpur-842 001, India

Balramjee Sah

University Department of Chemistry, B.R.A. Bihar University, Muzaffarpur-842 001, India

Corresponding Author(s) : Ramjee Sah

ramjeebrabu@yahoo.co.in

Asian Journal of Chemistry, Vol. 25 No. 8 (2013): Vol 25 Issue 8
Article Published : March 19, 2013

Abstract

For the first time the conversion of trimeric (M₃S₄)⁴⁺ to tetrameric (M₄S₄)⁴⁺ core has been made for molybdenum complex. The complex, K₅[Mo₃S₄(CN)₉] (1) on using with strong reducing agent transform into K₈[Mo₄S₄(CN)₁₂] (2) in near quantitative yield. The diamagnetic complex (1) containing (Mo₃)₆ core can accommodate two electrons in its non bonding molecular orbital 2a₁ under reducing environment to give a complex ion [Mo₃S₄(CN)₉]^7- with [Mo₃]₈ electronic configuration. This reduced species undergoes re-oxidation by atmospheric air to give back the original compound with [Mo₃]₆ core via a partially oxidized an intermediate species [Mo₃S₄(CN)₉]^6- with [Mo₃]₇ core shows a characteristic EPR signal. However, under drastic reducing condition, the two electrons reduced species [Mo₃S₄(CN)₉]^7- with [Mo₃]⁸ core accommodate the next coming electron to its anti-bonding two electron orbital and thus achieve an unstable trinuclear [Mo₃^III]⁹ core, where each metal centre has been reduced by one electron. The highly unstable and super reduced species [Mo₃S₄(CN)₉]^8- with [Mo₃^III]⁹ configuration undergoes core transformation from cuboidal trinuclear [Mo₃^IVS₄]⁴⁺ to the cubane type tetranuclear core [Mo₄^IIIS₄]⁴⁺ of [Mo₄S₄(CN)₁₂]^8- complex ion. The corresponding tungsten-analogue though responses this reduction, but quickly oxidizes back to the starting material during work-up procedure.

Keywords

Core conversion Trinuclear-cuboidal Tetra-nuclear cubane type Molybdenum-sulfur cluster

Sah, R., & Sah, B. (2013). K8[Mo4S4(CN)12]·4H2O: A New Alternative Synthetic Route for its Formation by Core Conversion from Trimer to Tetramer. Asian Journal of Chemistry, 25(8), 4487–4492. https://doi.org/10.14233/ajchem.2013.14026

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References

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A.J. Bard and L.R. Faulkner, Electrochemical Methods (New York; Wiley) (1980).

B.E. Bursten, F.A. Cotton, M.B. Hall and R.C. Najjar, J. Am. Chem. Soc., 104, 302 (1982).

(a) F.A. Cotton and X. Fung, Inorg. Chem., 30, 3666 (1991); (b) D.T. Richews and A.G. Sykes, Inorg. Chem., 21, 418, (1982); (c) M.T. Paffett and F.C. Asnon, Inorg. Chem., 22, 1547 (1983).

(a) Y. Ide and T. Shibahara, Inorg. Chem., 46, 357 (2007); (b) T. Yamauchi, H. Takagi, Shibahara and H. Akashi, Inorg. Chem., 45, 5429 (2006).

(a) H. Akashi, K. Isobe and T. Shibahara, Inorg. Chem., 44, 3494 (2005); (b) Y. Ide, M. Sasaki, M. Maeyama and T. Shibahara, Inorg. Chem., 43, 602 (2004).

(a) T. Shibahara and H. Kuroya,Polyhedron, 5, 357, (1986); (b) T. Shibahara, H. Akashi and H. Kuroya, J. Am. Chem. Soc., 108, 1342 (1986).

N.C. Howladir, G.P. Haight, T.W. Hambley, G.A. Lawrance, K.M. Rahmoiller and M.K. Show, Aust. J. Chem., 36, 377 (1983).

K. Weighardt, W. Herrman, A. Miller, W. Elzner and Z. Zimmermann, Naturforsch, B 39, 876 (1984).

(a) T. Shibahara, M. Tsuboi, S. Nakaska and Y. Ide, Inorg. Chem., 42, 935 (2003); (b) S.-B. Yu, M. Droege, B. Segal, S.-H. Kim, T. Sanderson and A.D. Watson, Inorg. Chem., 39, 1325 (2000).

T. Shibahara and H. Kuroya, Abstract of Papers "International Mini Conference for Young Chemist in Tokyo-Mamo Cyclic and Coordination Chemistry" (July, 1987).

T. Shibahara, H. Akashi and H. Kuroya, J. Am. Chem. Soc., 110, 3313 (1988).

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T. Shibaha, Proceeding of the 26th International Coordination Chemistry Conference, Oporto, Portugal, Paper A 27 (1988).

T. Shibahara, T. Yamamoto, H. Kanadani and H. Kuroya, J. Am. Chem. Soc., 109, 3495 (1987).

G. Christou, C.D. Garner, F.E. Maabs and T.J. King, J. Chem. Soc. Chem. Commun., 740 (1978).

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G. Christou and C.D. Garner, J. Chem. Soc. Dalton Trans., 2354 (1980).

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A. Miller, R. Jostes, W. Eltzner, E. Diemann, H. Bogge M. Zimmermann, M. Dartmann and B.N. Cyvin, Inorg. Chem., 24, 2872 (1985).

(a) P.K. Mascharak, Inorg. Chem., 25, 245 (1986); (b) G. Sakane, K. Hashimoto, M. Takashi, M. Takede and T. Shibahara, Inorg. Chem., 37, 4231 (1998).

S. Sarkar, R. Sah, P.K. Chaudhary, R. Maiti and S.K. Das, Proc. Indian Acad. Sci. (Chem. Sci.), 107, 355 (1995).