The Preparation of Silylamide Hauser Base (r 2 Nmgx; X = Halide) and Amido-grignard (r 2 Nmgr) Com- Plexes from Simple Grignard Reagents Using [k{n(sime 2

The preparation of silylamide Hauser base (R2NMgX; X = halide) and amido-Grignard (R2NMgR) complexes from simple Grignard reagents using [K{N(SiMe2 Bu)2}]n, [K{N(SiMe2 Bu)(SiPr3)}]n and [K{N(Si 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)(μ-Cl)(THF)]2 (N RR’ = {N(SiBuMe2)2} , 1; {N(SiBuMe2)(Si Pr3)} , 2; {N(SiPr3)2} , 3) and [Mg{N(SiPr3)2}(μ-C3H5)]∞ (4) identified as minor products. In contrast, salt metathesis protocols using potassium silylamides and methylmagnesium iodide gave [Mg(N)(μ-CH3)]2 (N = {N(SiBuMe2)2}, 7a; {N(SiBuMe2)(SiPr3)}, 8; {N(SiPr3)2} , 9) and [Mg{N(SiBuMe2)2}(CH3)(DME)] (7b), with [Mg{N(Si 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 under the conditions we employed. The synthesis of [Na{N(SiBuMe2)2}(THF)]2 (5a) and [Na{N(Si BuMe2)2}(DME)2] (5b) from benzyl sodium and HN(Si BuMe2)2, and a solvent-free structure of [K{N(SiBuMe2)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.