Alkaline earth complexes of silylated aminopyridinato ligands: homoleptic compounds and heterobimetallic coordination polymers

Ortu, Fabrizio, Moxey, Graeme J., Blake, Alexander J., Lewis, William and Kays, Deborah L. ORCID: https://orcid.org/0000-0002-4616-6001 2013. Alkaline earth complexes of silylated aminopyridinato ligands: homoleptic compounds and heterobimetallic coordination polymers. Inorganic Chemistry 52 (21) , pp. 12429-12439. 10.1021/ic4012923

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Abstract

The synthesis and characterization of magnesium and calcium complexes of sterically demanding aminopyridinato ligands is reported. The reaction of the 2-Me3SiNH-6-MeC5H3N (L1H), 2-MePh2SiNH-6-MeC5H3N (L2H), and 2-Me3SiNH-6-PhC5H3N (L3H) with KH in tetrahydrofuran (THF) yielded potassium salts L1K(thf)0.5 (1), L2K (2), and L3K(thf)0.5 (3), which, through subsequent reaction with MgI2 and CaI2, afforded the homoleptic complexes (L)2Ae(thf)n [L = L1, Ae = Mg, n = 1 (4); L = L2, Ae = Mg, n = 0 (5); L = L3, Ae = Mg, n = 0 (6); L = L2, Ae = Ca, n = 2 (7)] and heterobimetallic calciates {[(L)3Ca]K}∞ [L = L1 (8); L = L2 (9)]. The solid state structure of 8 reveals a polymeric arrangement in which the calciate units are interlocked by bridging potassium ions. Metalation reactions between L1H or L2H and (nBu)2Mg lead to the solvent-free compounds (L)2Mg [L = L1 (10); L = L2 (5)]. The bridged butyl mixed-metal complex [(L1)Li(μ2-nBu)Mg(L1)]∞ (11) was also obtained via a cocomplexation reaction with nBuLi and (nBu)2Mg. 11, which adopts a monodimensional polymeric array in the solid state, is a rare example of an alkyl-bridged Li/Mg complex and the first complex to feature an unsupported bridging butyl interaction between two metals. Changing the cocomplexation reaction conditions, the order of reagents added to the reactions mixture, and with the use of a coordinating solvent (tetrahydrofuran) formed the magnesiate complex (L1)3MgLi(thf) (12).

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	American Chemical Society
ISSN:	0020-1669
Last Modified:	12 Jul 2024 10:45
URI:	https://orca.cardiff.ac.uk/id/eprint/170326

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