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Structural Characterization of Lithium and Sodium Bulky Bis(silyl)amide Complexes

School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK
Author to whom correspondence should be addressed.
Molecules 2018, 23(5), 1138;
Received: 10 April 2018 / Revised: 3 May 2018 / Accepted: 4 May 2018 / Published: 10 May 2018
(This article belongs to the Special Issue Main Group Elements in Synthesis)
Alkali metal amides are vital reagents in synthetic chemistry and the bis(silyl)amide {N(SiMe3)2} (N′′) is one of the most widely-utilized examples. Given that N′′ has provided landmark complexes, we have investigated synthetic routes to lithium and sodium bis(silyl)amides with increased steric bulk to analyse the effects of R-group substitution on structural features. To perform this study, the bulky bis(silyl)amines {HN(SitBuMe2)(SiMe3)}, {HN(SiiPr3)(SiMe3)}, {HN(SitBuMe2)2}, {HN(SiiPr3)(SitBuMe2)} and {HN(SiiPr3)2} (1) were prepared by literature procedures as colourless oils; on one occasion crystals of 1 were obtained. These were treated separately with nBuLi to afford the respective lithium bis(silyl)amides [Li{μ-N(SitBuMe2)(SiMe3)}]2 (2), [Li{μ-N(SiiPr3)(SiMe3)}]2 (3), [Li{N(SitBuMe2)2}{μ-N(SitBuMe2)2}Li(THF)] (4), [Li{N(SiiPr3)(SitBuMe2)}(DME)] (6) and [Li{N(SiiPr3)2}(THF)] (7) following workup and recrystallization. On one occasion during the synthesis of 4 several crystals of the ‘ate’ complex [Li2{μ-N(SitBuMe2)2}(μ-nBu)]2 (5) formed and a trace amount of [Li{N(SiiPr3)2}(THF)2] (8) was identified during the recrystallization of 7. The reaction of {HN(SitBuMe2)2} with NaH in the presence of 2 mol % of NaOtBu gave crystals of [Na{μ-N(SitBuMe2)2}(THF)]2 (9-THF), whilst [Na{N(SiiPr3)2}(C7H8)] (10) was prepared by deprotonation of 1 with nBuNa. The solid-state structures of 110 were determined by single crystal X-ray crystallography, whilst 24, 7, 9 and 10 were additionally characterized by NMR and FTIR spectroscopy and elemental microanalysis. View Full-Text
Keywords: bis(silyl)amide; ligand; lithium; sodium bis(silyl)amide; ligand; lithium; sodium
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MDPI and ACS Style

Nicholas, H.M.; Goodwin, C.A.P.; Kragskow, J.G.C.; Lockyer, S.J.; Mills, D.P. Structural Characterization of Lithium and Sodium Bulky Bis(silyl)amide Complexes. Molecules 2018, 23, 1138.

AMA Style

Nicholas HM, Goodwin CAP, Kragskow JGC, Lockyer SJ, Mills DP. Structural Characterization of Lithium and Sodium Bulky Bis(silyl)amide Complexes. Molecules. 2018; 23(5):1138.

Chicago/Turabian Style

Nicholas, Hannah M., Conrad A.P. Goodwin, Jon G.C. Kragskow, Selena J. Lockyer, and David P. Mills. 2018. "Structural Characterization of Lithium and Sodium Bulky Bis(silyl)amide Complexes" Molecules 23, no. 5: 1138.

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