1,8-Bis(silylamido)naphthalene complexes of magnesium and zinc synthesised through alkane elimination reactions

Abstract

The reactions between magnesium or zinc alkyls and 1,8-bis(triorganosilyl)diaminonaphthalenes afford the 1,8-bis(triorganosilyl)diamidonaphthalene complexes with elimination of alkanes. The reaction between 1,8-C₁₀H₆(NSiMePh₂H)₂ and one or two equivalents of MgⁿBu₂ affords two complexes with differing coordination environments for the magnesium; the reaction between 1,8-C₁₀H₆(NSiMePh₂H)₂ and MgⁿBu₂ in a 1 : 1 ratio affords 1,8-C₁₀H₆(NSiMePh₂)₂{Mg(THF)₂} (1), which features a single magnesium centre bridging both ligand nitrogen donors, whilst treatment of 1,8-C₁₀H₆(NSiR₃H)₂ (R₃ = MePh₂, ⁱPr₃) with two equivalents of MgⁿBu₂ affords the bimetallic complexes 1,8-C₁₀H₆(NSiR₃)₂{ⁿBuMg(THF)}₂ (R₃ = MePh₂2, R₃ = ⁱPr₃3), which feature four-membered Mg₂N₂ rings. Similarly, 1,8-C₁₀H₆(NSiⁱPr₃)₂{MeMg(THF)}₂ (4) and 1,8-C₁₀H₆(NSiMePh₂)₂{ZnMe}₂ (5) are formed through reactions with the proligands and two equivalents of MMe₂ (M = Mg, Zn). The reaction between 1,8-C₁₀H₆(NSiMePh₂H)₂ and two equivalents of MeMgX affords the bimetallic complexes 1,8-C₁₀H₆(NSiMePh₂)₂(XMgOEt₂)₂ (X = Br 6; X = I 7). Very small amounts of [1,8-C₁₀H₆(NSiMePh₂)₂{IMg(OEt₂)}]₂ (8), formed through the coupling of two diamidonaphthalene ligands at the 4-position with concomitant dearomatisation of one of the naphthyl arene rings, were also isolated from a solution of 7.