From Simple Alkali Metal Silanolates to Heterometallic Bismuth Oxo Clusters Mehring, M.,* Nolde, C., Mansfeld, D. and Schürmann, M. Lehrstuhl für Anorganische Chemie II der Universität Dortmund, D-44221 Dortmund, Germany. (Tel./ Fax: (49) 231-7553835 / 7555048, E-mail: [email protected]) Bismuth-containing materials are associated with a variety of applications such as high-Tc superconductivity, oxide ion conduction, specialized glasses, pigments, thermoelectric devices, catalysts and ferroelectric devices.1,2 Homo- and heterometallic bismuth alkoxides are well known precursors for heterometallic metal oxide materials, but in contrast to the alkoxides the corresponding bismuth silanolates have been studied only briefly.3-5 In this communication we report results on our attempts to prepare bismuth trimethylsilanolate via the metathesis route using alkali metal trimethylsilanolates. Instead of pure Bi(OSiMe3)3 several alkali metal-bismuth silanolate oxo clusters were isolated. In addition we report novel clusters of partially hydrolyzed sodium trimethylsilanolate. The structures presented here demonstrate the diversity of the coordination geometry which is realized by bismuth and sodium in metal oxo clusters. A Lithium Bismuth Oxo Cluster The X-ray single crystal structures of... Na8(OSiMe3)4(HOSiMe3)4(OH)4·4THF 3 Bi(OtBu)3 + 6 LiOSiMe3 Si Na11(OSiMe3)3(HOSiMe3)9(OH)6(CO3) - LiOtBu Na - 2 Me3SiOSiMe3 Na−O 2.34 - 2.76 Å O(H)···O 2.65 - 2.70 Å O Si Li5Bi3(O)2(OSiMe3)2(OtBu)8 O Na Si O Li Bi NaOSiMe3 - anhydrous Na11(OSiMe3)10(OH)[6] J. F. Hyde et al. J. Am. Chem. Soc. 1953, 75, 5615 Na−O 2.24 - 2.80 Å O(H)···O 2.43 - 2.53 Å Si O W. S. Tatlock, E. G. Rochow J. Org. Chem. 1952, 17, 1555 Na [NaOSiMe]4 · 4HMPA O. V. Konov et al. Organomet. Chem. USSR 1991, 4, 784 Na−O 2.20 - 2.82 Å O(H)···O > 2.98 Å Bi - Li - O Core Structure NaOSiMe3·3H2O I. L. Dubchak et al. Zh. Strukt. Khim. 1982, 23, 63 ... demonstrate the affinity of NaOSiMe3 towards water and its tendency to aggregate upon partial hydrolysis. [NaOSiPh3]4·3H2O Li−O 1.88 - 2.10 Å Bi−O 2.09 - 2.67 Å K. Dehnicke et al. Z. Naturforsch. B 1996, 1584 Bismuth Trimethylsilanolate... BiCl3 + ... was prepared in 1968.4 Our attempts to synthesize Bi(OSiMe3)3 gave three heterometallic clusters instead. 10 NaOSiMe3 + 2 BiCl3 - 6 NaCl - Me3SiOSiMe3 Na4Bi2O(OSiMe3)8 3 NaOSiMe3 thf, moisture toluene Na5Bi10O7(OSiMe3)15(OH)6 Na4Bi18O20(OSiMe3)18 Si Si Bi Bi Na O Na Na/Bi−O 2.29 - 2.42 Å Na/Bi disorder O Na Si O Bi Na−O 2.32 - 2.67 Å Bi−O 2.01 - 3.01 Å References References [1] [1] C. C.A. A.Paz Pazde deAraujo, Araujo, J. J.D. D. Cuchiaro, Cuchiaro,L. L. D. D. McMillan, McMillan, M. M. C. C. Scott, Scott,J. J. F. F. Scott, Scott,Nature Nature2001, 2001, 374, 374, 627. 627. [2] [2] K. K. H. H.Whitmire, Whitmire,Chemtracts Chemtracts--Inorg. Inorg. Chem. Chem. 1995, 1995, 7, 7,167. 167. [3] [3] K. K.W. W.Terry, Terry, K. K.Su, Su, T. T.D. D. Tilley, Tilley, Polyhedron Polyhedron1998, 1998, 17, 17, 891. 891. [4] [4] H. H.Schmidbaur, Schmidbaur, M. M. Bergfeld, Bergfeld, Z. Z. Anorg. Anorg.Allg. Allg. Chem. Chem. 1968, 1968, 85. 85. [5] [5] M.-C. M.-C. Massiani, Massiani,R. R. Papiernik, Papiernik, L. L.G. G. Hubert-Pfalzgraf, Hubert-Pfalzgraf,J.-C. J.-C.Daran, Daran, Polyhedron Polyhedron1991, 1991, 10, 10, 437. 437. [6] I. L. Dubchak, V. E. Shklover, Yu. T. Struchkov, V. M. Kopylov, [6] I. L. Dubchak, V. E. Shklover, Yu. T. Struchkov, V. M. Kopylov, P. P. L. L.Prikhod‘ko, Prikhod‘ko, Zh. Zh. Strukt. Strukt.Khim Khim 1981, 1981, 24, 24, 59. 59. Na−O 2.15 - 3.01 Å Bi−O 2.05 - 3.29 Å Acknowledgements Acknowledgements The The Deutsche Deutsche Forschungsgemeinschaft, Forschungsgemeinschaft, the the Fonds Fonds der der Chemischen Chemischen Industrie Industrie and and Prof. Prof. Dr. Dr. K. K. Jurkschat Jurkschat is is gratefully gratefully acknowledged acknowledged for for support support of of this this work. work.
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