A functional model for lanthanide doped silicate materials: synthesis of an apically substituted samarium silsesquioxane complex

Arnold, P., Blake, A. J., Hall, S. N., Ward, B. D. and Wilson, C. (2001) A functional model for lanthanide doped silicate materials: synthesis of an apically substituted samarium silsesquioxane complex. Journal of the Chemical Society: Dalton Transactions, 2001(4), pp. 488-491. (doi: 10.1039/b009123p)

Abstract

Steric protection of a trisilanol silsesquioxane (also referred to as a silasesquioxane) by one TBDMS group (SiMe2But) generated a new siloxanolate ligand, (c-C5H9)7Si7O9(OH)2(OTBDMS) 1, that allows only restricted access to a co-ordinated metal. Lithiation afforded the stable complex (c-C5H9)7Si7O9(OLi)2(OTBDMS), which has allowed the generation of a samarium adduct [Sm(OC6H3But2-2,6){(c-C5H9)7Si7O9(O)(OLi)(OTBDMS)}2]. A structural study of this samarium adduct revealed two unusual features: an absence of stabilising M–O interactions with the siloxane core, and retention of one apical aryloxide group at the trivalent metal, through which the chemistry of a silica-functionalised Ln3+ ion might be modelled. X-Ray crystallography also revealed the dimeric hydrogen bonded structure of the disilanol ligands. The disilanol ligand 1 may also readily be converted into a dithallium salt, providing a potential precursor for further f-element derivatives of this disilanolate moiety.

• Item Type: Articles
• Additional Information: The authors thank the EPSRC and the Royal Society for support, the Nuffield Foundation for an Undergraduate Bursary NUF-URB99 (S. N. H.), and the EPSRC National Crystallography and National Mass Spectrometry Services.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Wilson, Dr Claire
• Authors: Arnold, P., Blake, A. J., Hall, S. N., Ward, B. D., and Wilson, C.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Journal of the Chemical Society: Dalton Transactions
• Publisher: Royal Society of Chemistry
• ISSN: 0300-9246
• ISSN (Online): 2050-5671
• Published Online: 01 January 2001