Sterically shielded primary anilides of the alkaline-earth metals of the type (thf)nAe(NH-Ar*)2 (Ae = Mg, Ca, Sr, and Ba; Ar* = bulky aryl).

ABSTRACT

Metalation of 2,4,6-triphenylphenylamine (H2N-C6H2-2,4,6-Ph3, 1a) and 4-methyl-2,6-bis(diphenylmethyl)aniline (2,6-bis(diphenylmethyl)-p-toluidine, H2N-C6H2-4-Me-2,6-(CHPh2)2, 2a) with dibutylmagnesium and Ae[N(SiMe3)2]2 with a stoichiometric 1 2 ratio in THF at room temperature yields the corresponding primary anilides [(thf)nAe{N(H)-C6H2-2,4,6-Ph3}2] (Ae/n = Mg/2 (1b), Ca/2 (1c), Sr/3 (1d), and Ba/3 (1e)) and [(thf)nAe{N(H)-C6H2-4-Me-2,6-(CHPh2)2}2] (Ae/n = Mg/2 (2b), Ca/3 (2c) and Sr/2 (2d)), respectively. The 1 1 reaction of Mg(n/sBu)2 and MgPh2 with 2a leads to the formation of heteroleptic [(thf)2Mg(R){N(H)-C6H2-4-Me-2,6-(CHPh2)2}] (R = n/sBu (2bBu), Ph (2bPh)). At 50 °C, the strontium complex 2d liberates one equivalent of 2avia intramolecular deprotonation of the triarylmethyl functionality yielding dinuclear [(thf)2Sr{N(H)-C6H2-4-Me-2-(CPh2)-6-(CHPh2)2}]2 (2d'). The barium compound is significantly more reactive and regardless of applied stoichiometry the isotypic barium congener [(thf)2Ba{N(H)-C6H2-4-Me-2-(CPh2)-6-(CHPh2)2}]2 (2e') forms. The molecular structures of 1c, 2d, 2d', and 2e' are stabilized by metal-phenyl π-interactions.