Cooperative Metal-Ligand Hydroamination Catalysis Supported by C-H Activation in Cyclam Zr(IV) Complexes

Inorganic Chemistry
Luis G AlvesAna M Martins

Abstract

Complexes of the type (R2Cyclam)ZrCl2 (where R = CH2═C(H)CH2 (All), CH2═C(Me)CH2 (MeAll), and PhCH2 (Bn)) react with suitable Grignard reagents to produce the corresponding alkyl derivatives (R2Cyclam)ZrR'2 (R' = Me, CH2Ph). Thermally induced double metalation of the pending arms of the cyclam ligand led to the formation of complexes ((CH═C(H)CH2)2Cyclam)Zr, 14, ((CH═C(Me)CH2)2Cyclam)Zr, 15, or ((C6H4CH2)2Cyclam)Zr, 16. These reactions proceed through C(sp2)-H bond activation and R'H elimination and convert the original dianionic tetracoordinated cyclam-based ligands in tetraanionic hexacoordinated ligands that establish two new Zr-C bonds. The cleavage of the Zr-C bonds may be readily achieved by treatment of the bis( ortho-metalated) species 16 with protic substrates ( tert-butanol, phenol, thiophenol, aniline, benzophenone hydrazone, pyrazole, and N, N'-diphenylhydrazine), to give rise to (Bn2Cyclam)ZrX2 complexes (X = OtBu, OPh, SPh, NHPh, NHNCPh2, C3H3N2, N, N'-PhNNPh). In catalytic conditions, complexes (All2Cyclam)Zr(NMe2)2, 14, 15, or 16 convert 2,2-diphenyl-pent-4-enylamine to 2-methyl-4,4-diphenylpyrrolidine with 100% selectivity and conversion values varying between 61 and 88% in 4.5 h, at 115 °C. Complexes 14 and 15...Continue Reading

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