Synthesis, Structure, and Properties of Magnesium Complexes Containing Mixed Cyclopentadienyl and Amido Ligand Sets

[CpMgMe(Et 2 O)] 2 was prepared by dissolving Cp 2 Mg and dimethylmagnesium together in diethyl ether. It reacted readily with diphenylamine, 3-amino-2,4-dimethylpentane, 2,6-diisopropylaniline, N -isopropylbenzylamine, and diisopropylamine in diethyl ether to afford the dimeric amido complexes [CpMg(NPh 2 )] 2 (83%), [CpMg(NHCH(CH(CH 3 ) 2 ) 2 )] 2 (75%), [CpMg(NH i Pr 2 C 6 H 3 )] 2 (61%), [CpMg(N( i Pr)(CH 2 Ph))] 2 (62%), and [CpMg(N i Pr 2 )] 2 (81%) as colorless crystalline solids. Treatment of [CpMgMe(Et 2 O)] 2 with N, N, N ‘-trimethylethylenediamine in diethyl ether yielded dimeric [CpMg(MeNCH 2 CH 2 NMe 2 )] 2 (76%). The reaction of [CpMgMe(Et 2 O)] 2 with 2,5-bis(dimethylaminomethyl)pyrrole in diethyl ether led to the formation of the monomeric magnesium pyrrolato complex [CpMg(Et 2 O)(η 2 -Me 2 NCH 2 (C 4 H 2 N)CH 2 NMe 2 )] (70%). The X-ray crystal structures of [CpMg(NPh 2 )] 2, [CpMg(NHCH(CH(CH 3 ) 2 ) 2 )] 2, [CpMg(NH i Pr 2 C 6 H 3 )] 2, [CpMg(N( i Pr)(CH 2 Ph))] 2, and [CpMg(Et 2 O)(η 2 -Me 2 NCH 2 (C 4 H 2 N)CH 2 NMe 2 )] were determined. In the solid state structures, [CpMg(NPh 2 )] 2, [CpMg(NHCH(CH(CH 3 ) 2 ) 2 )] 2, [CpMg(NH i Pr 2 C 6 H 3 )] 2, and [CpMg(N( i Pr)(CH 2 Ph))] 2 contain one η 5 -cyclopentadienyl ligand per magnesium and almost perfectly square Mg 2 N 2 cores. The complex [CpMg(Et 2 O)(η 2 -Me 2 NCH 2 (C 4 H 2 N)CH 2 NMe 2 )] contains one η 5 -cyclopentadienyl ligand, one diethyl ether ligand, and one η 2 -2,5-bis(dimethylaminomethyl)pyrrolato ligand.