title: Alkaline earth complexes of silylated aminopyridinato ligands: homoleptic compounds and heterobimetallic coordination polymers.
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 (L(1)H), 2-MePh2SiNH-6-MeC5H3N (L(2)H), and 2-Me3SiNH-6-PhC5H3N (L(3)H) with KH in tetrahydrofuran (THF) yielded potassium salts L(1)K(thf)0.5 (1), L(2)K (2), and L(3)K(thf)0.5 (3), which, through subsequent reaction with MgI2 and CaI2, afforded the homoleptic complexes (L)2Ae(thf)n [L = L(1), Ae = Mg, n = 1 (4); L = L(2), Ae = Mg, n = 0 (5); L = L(3), Ae = Mg, n = 0 (6); L = L(2), Ae = Ca, n = 2 (7)] and heterobimetallic calciates {[(L)3Ca]K}∞ [L = L(1) (8); L = L(2) (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 L(1)H or L(2)H and ((n)Bu)2Mg lead to the solvent-free compounds (L)2Mg [L = L(1) (10); L = L(2) (5)]. The bridged butyl mixed-metal complex [(L(1))Li(μ2-(n)Bu)Mg(L(1))]∞ (11) was also obtained via a cocomplexation reaction with (n)BuLi and ((n)Bu)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 (L(1))3MgLi(thf) (12).
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham NG7 2RD, United Kingdom.
authors.forename: Fabrizio
authors.initials: F
authors.lastname: Ortu
authors.forename: Graeme J
authors.initials: GJ
authors.lastname: Moxey
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.forename: William
authors.initials: W
authors.lastname: Lewis
authors.forename: Deborah L
authors.initials: DL
authors.lastname: Kays
mesh_terms: D000631:Aminopyridines / Q000737:chemistry*; D002118:Calcium / Q000737:chemistry*; D060326:Chemistry Techniques, Synthetic; D056831:Coordination Complexes; D018360:Crystallography, X-Ray; D008024:Ligands; D008274:Magnesium / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D012997:Solvents
chemical_list: D000631:Aminopyridines; D056831:Coordination Complexes; D008024:Ligands; D009942:Organometallic Compounds; D012997:Solvents; C434823:n-butyllithium; D008274:Magnesium; D002118:Calcium