Bicyclic Guanidinates in Mono- and Di-Valent Metal Complexes, Including Group 1/2 and Group 1/12 Heterometallic Systems
AUSTRALIAN JOURNAL OF CHEMISTRY（2013）
Abstract
Complexes containing mono-, di-, and mixed mono-/di-valent metal centres supported by the [hpp](-) anion (hppH = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) are reported. Amine elimination from Mn(N{SiMe3}(2))(2) using the neutral guanidine is a clean route to the heteroleptic compound [Mn(hpp)(N{SiMe3}(2))](2). Addition of 18-crown-6 to a solution of the hpp- potassium salt (hppK) enables the first potassium derivative of [hpp](-) to be structurally analysed, showing that the crown ether restricts aggregation to afford a monometallic structure. Mixed lithium-magnesium and lithium-zinc compounds of general formula Li2M2(hpp)(6) (M = Mg, Zn) have been characterised crystallographically showing the guanidinate anions to be present in two different coordination modes, bridging two-or four-metal centres. Spectroscopic measurements suggest a robust framework that is maintained in solution.
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