Exchanged ligands on the surface of a giant cluster: [(MoO₃)₁₇₆(H₂O)₆₃(CH₃OH)₁₇H_n]^{(32 – n)–}

Abstract

The synthesis of 1a·(32 – n)Na⁺·ca. 600 H₂O·ca. 30 CH₃OH 1 containing the ring-shaped, mixed-valence (Mo^V/Mo^VI) cluster [(MoO₃)₁₇₆(H₂O)₆₃(CH₃OH)₁₇H_n]^{(32 – n)–} 1a as a discrete unit in the crystal lattice is reported, which for the first time yields a compound of this type via a facile synthetic method and without amorphous reaction products; remarkably, H₂O ligands can be replaced by CH₃OH on the surface of a giant metal-oxide based cluster which has a nanometer sized cavity and, in contrast to zeolites, reducing properties.

References

1. A. Müller, E. Krickemeyer, J. Meyer, H. Bögge, F. Peters, W. Plass, E. Diemann, S. Dillinger, F. Nonnenbruch, M. Randerath and C. Menke, Angew. Chem., Int. Ed. Engl., 1995, 34, 2122.
2. A. Müller, F. Peters, M. T. Pope and D. Gatteschi, Chem. Rev., 1998, 98, 239.
3. A. Müller, E. Krickemeyer, H. Bögge, M. Schmidtmann, C. Beugholt, P. Kögerler and C. Lu, Angew. Chem., Int. Ed. Engl., 1998, 37, 1220.
4. A. Müller, J. Meyer, E. Krickemeyer and E. Diemann, Angew. Chem., Int. Ed. Engl., 1996, 35, 1206.
5. M. B. Robin and P. Day, Adv. Inorg. Chem. Radiochem., 1967, 10, 247.
6. A. Müller, E. Krickemeyer, H. Bögge, M. Schmidtmann, F. Peters, C. Menke and J. Meyer, Angew. Chem., Int. Ed. Engl., 1997, 36, 484.
7. M. I. Khan and J. Zubieta, J. Am. Chem. Soc., 1992, 114, 10 058; H. K. Chea, W. G. Klemperer and T. A. Marquart, Coord. Chem. Rev., 1993, 128, 209.
8. K. Wassermann, M. H. Dickman and M. T. Pope, Angew. Chem., Int. Ed. Engl., 1997, 36, 1445.
9. Gmelins Handbuch der Anorganischen Chemie, Verlag Chemie, Berlin, 1935: Mo, pp. 134–137.
10. Gmelin Handbook of Inorganic Chemistry, Springer, Berlin, 1989: Mo Suppl. B3, pp. 61–68.