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

The dimeric copper(I) 3-sila-β-diketiminate [Cu{(N(R)C(Ar))2SiR}]2 · (thf) (1) was obtained from CuI and [Li{(N(R)C(Ar))2SiR}(thf)2] (B) in toluene (R = SiMe3, Ar = C6H3Me2-2,6). When [CuI(PPh3)3] was used as a starting material, the LiI-containing compound [Cu{Si(R)(C(Ar)N(R))2Li(μ-I)}(PPh3)] (2) was isolated. The reaction of [MI(PPh3)n] (M = Ag, n = 3; M = Au, n = 2) with two equivalents of B in toluene gave the isomorphous silver and gold 3-sila-β-diketiminates [M{Si(R)(C(Ar)N(R))2Li}2(μ-I)] [M = Ag (3), Au (4)]. Each of 1–4 was characterised by the multinuclear NMR spectroscopy and single-crystal X-ray diffraction crystallography.

Reaction of the lithium 3-sila-β-diketiminate [Li{(N(R)C(Ar))2SiR}(thf)2] with CuI, [CuI(PPh3)3] or [MI(PPh3)n] (M = Ag, n = 3; M = Au, n = 2) gave the crystalline [Cu{(N(R)C(Ar))2SiR}]2 · (thf) (1), [Cu{Si(R)(C(Ar)N(R))2Li(μ-I)}(PPh3)] (2) or [M{Si(R)(C(Ar)N(R))2Li}2(μ-I)] [M = Ag (3), Au (4)], respectively. In each of 1–4 the ligand is Si-centred towards the coinage metal atom with additional N → Cu (1) or N → Li (2–4) coordination.Figure optionsDownload as PowerPoint slide