| People | Locations | Statistics |
|---|---|---|
| Naji, M. |
| |
| Motta, Antonella |
| |
| Aletan, Dirar |
| |
| Mohamed, Tarek |
| |
| Ertürk, Emre |
| |
| Taccardi, Nicola |
| |
| Kononenko, Denys |
| |
| Petrov, R. H. | Madrid |
|
| Alshaaer, Mazen | Brussels |
|
| Bih, L. |
| |
| Casati, R. |
| |
| Muller, Hermance |
| |
| Kočí, Jan | Prague |
|
| Šuljagić, Marija |
| |
| Kalteremidou, Kalliopi-Artemi | Brussels |
|
| Azam, Siraj |
| |
| Ospanova, Alyiya |
| |
| Blanpain, Bart |
| |
| Ali, M. A. |
| |
| Popa, V. |
| |
| Rančić, M. |
| |
| Ollier, Nadège |
| |
| Azevedo, Nuno Monteiro |
| |
| Landes, Michael |
| |
| Rignanese, Gian-Marco |
|
Liddle, Stephen
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (8/8 displayed)
- 2024Tris-Silanide f-Block Complexes:Insights into Paramagnetic Influence on NMR Chemical Shifts
- 2023Synthesis and Characterization of Yttrium Methanediide Silanide Complexescitations
- 2023Comparison of group 4 and thorium M(IV) substituted cyclopentadienyl silanide complexescitations
- 2023Comparison of group 4 and thorium M(IV) substituted cyclopentadienyl silanide complexescitations
- 202331P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium–Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal–Phosphorus Bond Ordercitations
- 2022Electronic Structure Comparisons of Isostructural Early d- and f-Block Metal(III) Bis(cyclopentadienyl) Silanide Complexescitations
- 2021Exceptional Uranium(VI)-Nitride Triple Bond Covalency from 15N Nuclear Magnetic Resonance Spectroscopy and Quantum Chemical Analysiscitations
- 2016Emergence of comparable covalency in isostructural cerium(IV)– and uranium(IV)–carbon multiple bonds
Places of action
| Organizations | Location | People |
|---|
article
Comparison of group 4 and thorium M(IV) substituted cyclopentadienyl silanide complexes
Abstract
We report the synthesis and characterisation of a series of M(IV) substituted cyclopentadienyl hypersilanide complexes of the general formula [M(Cp<sup>R</sup>)<sub>2</sub>{Si(SiMe<sub>3</sub>)<sub>3</sub>}(X)] (M = Hf, Th; CpR = Cp′, {C<sub>5</sub>H<sub>4</sub>(SiMe<sub>3</sub>)} or Cp′′, {C5H3(SiMe3)2-1,3}; X = Cl, C3H5). The separate salt metathesis reactions of [M(CpR)2(Cl)2] (M = Zr or Hf, CpR = Cp′; M = Hf or Th, CpR = Cp′′) with equimolar K{Si(SiMe3)3} gave the respective mono-silanide complexes [M(Cp′)2{Si(SiMe3)3}(Cl)] (M = Zr, 1; Hf, 2), [Hf(Cp′′)(Cp′){Si(SiMe3)3}(Cl)] (3) and [Th(Cp′′)2{Si(SiMe3)3}(Cl)] (4), with only a trace amount of 3 presumably formed via silatropic and sigmatropic shifts; the synthesis of 1 from [Zr(Cp′)2(Cl)2] and Li{Si(SiMe3)3} has been reported previously. The salt elimination reaction of 2 with one equivalent of allylmagnesium chloride gave [Hf(Cp′)2{Si(SiMe3)3}(η3-C3H5)] (5), whilst the corresponding reaction of 2 with equimolar benzyl potassium yielded [Hf(Cp′)2(CH2Ph)2] (6) together with a mixture of other products, with elimination of both KCl and K{Si(SiMe3)3}. Attempts to prepare isolated [M(CpR)2{Si(SiMe3)3}]+ cations from 4 or 5 by standard abstraction methodologies were unsuccessful. The reduction of 4 with KC8 gave the known Th(III) complex, [Th(Cp′′)3]. Complexes 2-6 were characterised by single crystal XRD, whilst 2, 4 and 5 were additionally characterised by 1H, 13C{1H} and 29Si{1H} NMR spectroscopy, ATR-IR spectroscopy and elemental analysis. In order to probe differences in M(IV)–Si bonds for d- and f-block metals we studied the electronic structures of 1-5 by density functional theory calculations, showing M–Si bonds of similar covalency for Zr(IV) and Hf(IV), and less covalent M–Si bonds for Th(IV).