Various new tris(pyrazolyl)alkanes of the class R'CTp (R' = Me, Et, Pr, iBu; R = Et, Pr, Cy, BuPh, Ph; Pr = cyclopropyl, Cy = cyclohexyl, BuPh = -butylphenyl) were synthesised and their reactivity towards Mg(AlMe) was examined. Along with new examples of recurring structural motifs, such as separated ion pairs and "metal in a box" complexes, , [(MeCTp)Mg][AlMe], several magnesium complexes with new structural features/compositions were obtained. Treatment of the "metal in a box" species [(MeCTp)Mg][AlMe] with THF donor gave the terminal methyl complex [(MeCTp)MgMe(thf)][AlMe]. Variation of the backbone alkyl substituent R' in the tris(pyrazolyl)alkane R'CTp gave ionic liquids (R' = Et, Pr) and the methyl-bridged dimagnesium complex [({iBuCTp}Mg{AlMe})(μ-Me)][AlMe]. The bulky Cy and BuPh moieties at the pyrazolyl 3 position gave the new structural motif [MeCTpMg(η-AlMe)][AlMe] (η, R = Cy; η, R = BuPh), stabilising a "[Mg(AlMe)]" entity. The AlMe group can be reversibly displaced under reduced pressure affording the new separated ion pair [(MeCTp)MgMe][AlMe] with a terminal "[MgMe]" moiety. Moderate thermal treatment of both [(MeCTp)MgMe][AlMe] and [(MeCTp)Mg(η-AlMe)][AlMe] resulted in selective C-H-bond activation in the 5 position of one of the pyrazolyl moieties and the formation of an AlMe-modified anionic tris(pyrazolyl)alkane and hence the neutral complex [MeC(pz)(pz)]MgMe.
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