The first structurally characterised oligosilylmagnesium compound

Synthesis of oligosilyldi- and trianions

“…In order to moderate the reactivity of the di-and trianions transmetalation with magnesium bromide was carried out [11]. However, even when a fairly large excess of magnesium bromide was used insoluble polymeric mixtures were obtained where the anions are connected via magnesium atoms.…”

Synthesis and structures of 3-sila-β-diketiminato complexes of the coinage metals

“…Its Si(1) and Li atoms act as a bridge to the Cu and I atoms, respectively. The endocyclic parameters of the boat are somewhat similar to those in L as shown by the following data for L: 9(2)°, C(4)-Si(1)-C(13) 108.8(1)°; and the dihedral angles between the N(1)C(13)-C(4)N(2) plane and the N(1)LiN(2) and C(13)Si(1)C(4) planes are 53.7(1)°and 28.4(1)°, respectively [7], which Table 1 Selected endocyclic geometric parameters for 1, four Cu I amidinates and a Cu I 1-azaallyl (R = SiMe 3 ) (6) 1.275 (7), 1.288 (7) 1.740 (5), 1.753 (5) 106.3(2), 110.9(2) 111.5(4), 114.4 (5) 132.1(4), 133.9(4) When the silver reaction was carried out using an equimolar portion of the two reagents, approximately one half of the unreacted [AgI(PPh 3 ) 3 ] was recovered. A freshly prepared sample of 3 or 4 in C 6 D 6 gave 1 H NMR spectra showing the appropriate relative intensities for signals corresponding to the ligand; and the 29 Si spectra of 3 revealed coupling of the 29 Si nucleus to both 107 Ag and 109 Ag, as expected from the molecular structure shown for crystalline 3.…”

“…X-ray structural data are available for [Li{(N(R)@C(Ar)) 2 SiR}(NCAr) 2 ] [4], [Li{(N(R)@C(Ar)) 2 -SiR}(NCAr)] [7], C1 [6], C2 [7], D [6], E2 [7], E3 [7], E5 [7], F [7] and H [8]. Two further crystalline magnesium 3-sila-bdiketiminates have been reported: I from [Mg(SiR 3 ) 2 (thf) 2 ] [9] and 2ArCN, and J from I and Me 3 SiOTf [8].…”

Nucleophilicity of Neutral versus Cationic Magnesium Silyl Compounds

“…The compound (THF) 2 MgSi(SiMe 3 ) 3 Me 9 shows that mixed silyl alkyl magnesium complexes are isolable. Although the steric properties of the Si(SiMe 3 ) 3 versus the methyl group might be expected to dominate reactivity patterns, an initial data point from Marschner and co-workers suggests otherwise.…”

“…Although the steric properties of the Si(SiMe 3 ) 3 versus the methyl group might be expected to dominate reactivity patterns, an initial data point from Marschner and co-workers suggests otherwise. 9 The salt metathesis reaction of (THF) 2 3 Me final product. 10 Thus, the bulkier silyl group transfers faster than the methyl group, although both groups undergo transmetalation.…”