Group 2 metal (Mg, Ca, Sr) silylamides supported by a cyclen-derived macrocyclic polyamine

Abstract

Heteroleptic bis(silyl)amides of magnesium and calcium [(L)M{N(SiMe₃)₂}] [M = Mg, Ca; LH = 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane; (Me₃TACD)H] were previously synthesized from LH and [M{N(SiMe₃)₂}₂]. Strontium bis(silyl)amides [Sr{N(SiMe₃)₂}₂(thf)₂] and [Sr{N(SiHMe₂)₂}₂(thf)_2/3] reacted with LH to give different types of products, depending on the presence of the β-SiH function. While the former underwent protonolysis to give the amido-bridged dimer [(L)Sr{N(SiMe₃)₂}]₂ (1), the latter gave the adduct [(LH)Sr{N(SiHMe₂)₂}₂] (2) as a stable solid. 2 slowly underwent an intramolecular Si–H/H–N dehydrocoupling in solution to give [{(L)SiMe₂N(SiHMe₂)}Sr{N(SiHMe₂)₂}] (3) by liberating H₂. The results of transamination of 1 with HN(SiHMe₂)₂ depended on the relative stoichiometric ratio. A 1 : 1 mixture in n-pentane gave [{(L)SiMe₂N(SiHMe₂)}Sr{N(SiMe₃)₂}] (4) and H₂, while excess HN(SiHMe₂)₂ gave the adduct 2 under similar conditions. Compounds 2 and 3 exhibit Sr↼H–Si interactions according to X-ray crystallography, NMR, and IR spectroscopy. Lighter congeners of elusive [(L)Sr{N(SiHMe₂)₂}] were isolable for Mg (5) and Ca (6).