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

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 46; no. 12; pp. 4101 - 4110
• Main Authors: Bradley, Mark A, Birchall, Chris, Blake, Alexander J, Lewis, William, Moxey, Graeme J, Kays, Deborah L
• Format: Journal Article
• Language: English
• Published: England 21.03.2017
• Subjects: Alkanes; Bimetals; Coupling; Equivalence; Ligands; Magnesium; Nitrogen; Zinc
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c7dt00471k

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-C H (NSiMePh H) and one or two equivalents of Mg Bu affords two complexes with differing coordination environments for the magnesium; the reaction between 1,8-C H (NSiMePh H) and Mg Bu in a 1 : 1 ratio affords 1,8-C H (NSiMePh ) {Mg(THF) } (1), which features a single magnesium centre bridging both ligand nitrogen donors, whilst treatment of 1,8-C H (NSiR H) (R = MePh , Pr ) with two equivalents of Mg Bu affords the bimetallic complexes 1,8-C H (NSiR ) { BuMg(THF)} (R = MePh 2, R = Pr 3), which feature four-membered Mg N rings. Similarly, 1,8-C H (NSi Pr ) {MeMg(THF)} (4) and 1,8-C H (NSiMePh ) {ZnMe} (5) are formed through reactions with the proligands and two equivalents of MMe (M = Mg, Zn). The reaction between 1,8-C H (NSiMePh H) and two equivalents of MeMgX affords the bimetallic complexes 1,8-C H (NSiMePh ) (XMgOEt ) (X = Br 6; X = I 7). Very small amounts of [1,8-C H (NSiMePh ) {IMg(OEt )}] (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.