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Issue 14, 2016
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Salt metathesis versus protonolysis routes for the synthesis of silylamide Hauser base (R2NMgX; X = halogen) and amido-Grignard (R2NMgR) complexes

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Abstract

The preparation of silylamide Hauser base (R2NMgX; X = halide) and amido-Grignard (R2NMgR) complexes from simple Grignard reagents using [K{N(SiMe2tBu)2}]n, [K{N(SiMe2tBu)(SiiPr3)}]n and [K{N(SiiPr3)2}]n, and their parent silylamines, was explored. Both salt metathesis and protonolysis routes proved ineffective with allylmagnesium chloride as a starting material due to complex Schlenk equilibria, with [Mg(NRR′)(μ-Cl)(THF)]2 (NRR′ = {N(SitBuMe2)2}, 1; {N(SitBuMe2)(SiiPr3)}, 2; {N(SiiPr3)2}, 3) and [Mg{N(SiiPr3)2}(μ-C3H5)] (4) identified as minor products. In contrast, salt metathesis protocols using potassium silylamides and methylmagnesium iodide gave [Mg(NRR′)(μ-CH3)]2 (NRR′ = {N(SitBuMe2)2}, 7a; {N(SitBuMe2)(SiiPr3)}, 8; {N(SiiPr3)2}, 9) and [Mg{N(SitBuMe2)2}(CH3)(DME)] (7b), with [Mg{N(SitBuMe2)2}(μ-I)(THF)]2 (10) isolated as a side-product during the preparation of 7a. Unusually, methylmagnesium iodide, di-n-butylmagnesium and 7–9 did not react with HNRR′ under the conditions we employed. The synthesis of [Na{N(SitBuMe2)2}(THF)]2 (5a) and [Na{N(SitBuMe2)2}(DME)2] (5b) from benzyl sodium and HN(SitBuMe2)2, and a solvent-free structure of [K{N(SitBuMe2)2}] (6), are also reported. Complexes 1, 5b, 7a, 7b, 8, 9 and 10 are fully characterised by single crystal XRD, multinuclear NMR and IR spectroscopy and elemental analysis, whereas complexes 2–4, 5a and 6 were identified by XRD only.

Graphical abstract: Salt metathesis versus protonolysis routes for the synthesis of silylamide Hauser base (R2NMgX; X = halogen) and amido-Grignard (R2NMgR) complexes

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Supplementary files

Article information


Submitted
03 Jul 2015
Accepted
05 Aug 2015
First published
05 Aug 2015

This article is Open Access

Dalton Trans., 2016,45, 6004-6014
Article type
Paper

Salt metathesis versus protonolysis routes for the synthesis of silylamide Hauser base (R2NMgX; X = halogen) and amido-Grignard (R2NMgR) complexes

C. A. P. Goodwin, A. Smith, F. Ortu, Iñigo. J. Vitorica-Yrezabal and D. P. Mills, Dalton Trans., 2016, 45, 6004
DOI: 10.1039/C5DT02535D

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