Homoleptic tetrakis(silyl) complexes of Pd(0) and Pt(0) featuring metal-centred heterocubane structures: evidence for the existence of the corresponding mononuclear Pd(I) and Pt(I) complexes.

We report on the first homoleptic tetrakis(silyl) complexes of zerovalent Group 10 metals. The compounds [MLi4{Si(3,5-Me2pz)3}4] (M=Pd and Pt; 3,5-Me2 pz=3,5-dimethylpyrazolyl) exhibit very appealing metal-centred heterocubane structures with the central d(10) metal atoms surrounded by four silicon and four lithium atoms. Both compounds were characterised in detail, including X-ray crystal-structure analysis and 2D NMR spectroscopic methods such as (7)Li,(29 Si and (7)Li,(195)Pt HMQC.

Heterobimetallic cuprates consisting of a redox-switchable, silicon-based metalloligand: synthesis, structures, and electronic properties.

A series of bimetallic silyl halido cuprates consisting of the new tripodal silicon-based metalloligand [κ(3)N-Si(3,5-Me2pz)3Mo(CO)3](-) is presented (pz = pyrazolyl). This metalloligand is straightforwardly accessible by reacting the ambidentate ligand tris(3,5-dimethylpyrazolyl)silanide ({Si(3,5-Me2pz)3}(-)) with [Mo(CO)3(η(6)-toluene)]. The compound features a fac-coordinated tripodal chelating ligand and an outward pointing, "free" pyramidal silyl donor, which is easily accessible for a secondary coordination to other metal centers.

Syntheses, structures, and reactivity of poly(pyrazolyl)silanes, -disilanes, and the ambidentate kappa(1)Si/kappa(3)N-coordinating tris(3,5-dimethylpyrazolyl)silanide ligand [Si(3,5-Me2pz)3]- ((Me)Tpsd).

The reaction conditions for the synthesis [Si(2)((Me)pz)(6)] (1) and [Si((Me)pz)(4)] (4) have been investigated in detail in order to obtain suitable precursor compounds for the synthesis of the hitherto unknown Janus-head ligand tris(3,5-dimethylpyrazolyl)silanide ([Si((Me)pz)(3)](-), (Me)Tpsd). Within the monomeric lithium salt [Li(thf)((Me)Tpsd)] (5), the ambidentate silanide ligand is bound in a kappa(3)N-fashion to the Li cation, featuring an uncoordinated, anionic silicon bridgehead. Treatment of the silanide with various electrophiles such as Me(3)SiCl, Me(3)SnCl and Ph(3)SnCl gave in each case the expected salt metathesis reaction with the formation of Si-Si and Si-Sn bonds, respectively.

A triangulo palladium cluster consisting of μ3-capping silyl ligands.

We report on the utility of multifunctional, κ(1)Si:κ(3)S-coordinated tris(methimazolyl)silanide ligands [Si(mt(Me))(3)](-) for the stabilisation of a triangulo palladium cluster [Pd(3){Si(mt(Me))(3)}(2)] (3) consisting of very unusual μ(3)-capping SiR(3) donors. Differences to the corresponding platinum chemistry were supported by NMR spectroscopy and DFT calculations.

7Li,15N heteronuclear multiple quantum shift correlation-a fast and reliable 2D NMR method on natural abundant nuclei.

A straightforward natural abundance 2D HMQC NMR experiment between lithium-7 and nitrogen-15 is reported; this fast, reliable and routinely implementable method represents a powerful spectroscopic tool to study complex structures or intermediate species in solution, in particular those containing nitrogen-lithium bonds.

Multidentate ligand systems featuring dual functionality.

Multifunctional ligands with podand topology provide intrinsically well-defined coordination geometries. Several subgroups of multidentate ligand systems comprising dual functionality have been developed so far. Recent advances made in this research area reflect its topicality.