Salt metathesis versus protonolysis routes for the synthesis of silylamide Hauser base (R2NMgX; X = halogen) and amido-Grignard (R2NMgR) complexes.
The preparation of silylamide Hauser base (R2NMgX; X = halide) and amido-Grignard (R2NMgR) complexes from simple Grignard reagents using [K{N(SiMe2(t)Bu)2}]n, [K{N(SiMe2(t)Bu)(Si(i)Pr3)}]n and [K{N(Si(i)Pr3)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(N(RR'))(μ-Cl)(THF)]2 (N(RR') = {N(Si(t)BuMe2)2}(-), 1; {N(Si(t)BuMe2)(Si(i)Pr3)}(-), 2; {N(Si(i)Pr3)2}(-), 3) and [Mg{N(Si(i)Pr3)2}(μ-C3H5)]∞ (4) identified as minor products. In contrast, salt metathesis protocols using potassium silylamides and methylmagnesium iodide gave [Mg(N(RR'))(μ-CH3)]2 (N(RR') = {N(Si(t)BuMe2)2}(-), 7a; {N(Si(t)BuMe2)(Si(i)Pr3)}(-), 8; {N(Si(i)Pr3)2}(-), 9) and [Mg{N(Si(t)BuMe2)2}(CH3)(DME)] (7b), with [Mg{N(Si(t)BuMe2)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 HN(RR') under the conditions we employed. The synthesis of [Na{N(Si(t)BuMe2)2}(THF)]2 (5a) and [Na{N(Si(t)BuMe2)2}(DME)2] (5b) from benzyl sodium and HN(Si(t)BuMe2)2, and a solvent-free structure of [K{N(Si(t)BuMe2)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.
School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK. david.mills@manchester.ac.uk.
Conrad A P
CA
Goodwin
Alex
A
Smith
Fabrizio
F
Ortu
Iñigo J
IJ
Vitorica-Yrezabal
David P
DP
Mills