Oligophosphanide als Bausteine für phosphorreiche Komplexe und Heterocyclen
Final Report Abstract
The targeted synthesis of ions such as (P4R4)2–, (P4HR4)– (R = Ph, Mes) and cyclo- (P5But4)− as Li, Na or K salts and their versatile reactivity towards main group (groups 13-15) and transition metal complexes (Zr, Ta, Mn, Fe, Rh, groups 10-12) allowed the preparation of a large variety of phosphorus-rich metal oligophosphanides. In reactions with the anions (P4R4)2– or (P4HR4)– (R = Ph, Mes), complexes with intact (P4R4)2– or (P4HR4)– ligands are formed or degradation or oxidative coupling was observed resulting in complexes with (P3R3)2–, (P2R2)2–, and diphosphene (P2R2) or even (P6R6)2– ligands. On the other hand, in reactions with metal complexes the cyclo-(P5But4)− ion was observed to either stay intact or rearrange to cyclo-(P5But3), cyclo-(P4But3)−, {cyclo-(P4But3)PBut}− or {cyclo-(P5Bu4t)PBut}−, depending on the starting materials. In these reactions, the products formed are clearly influenced by the nature of the co-ligand of the metal complex, the metal, the reaction conditions and the stoichiometric ratio. The corresponding complexes can be used as precursors for the rational synthesis of phosphorus-rich binary metal phosphides (MxPy with y>x), which are expected to exhibit interesting properties for materials science. Metal phosphides have a wide range of applications such as corrosion resistors, catalysts for hydrodesulfurisation and hydrodenitrogenation, oxygen barriers, semiconductors, magnetic materials, anode materials in lithium ion batteries and nanoparticles.
Publications
- [Li(tmeda)2][cyclo-(P5But4)]: An unusual ion-separated lithium oligophosphanide. Chimie 13 (2010)
R. Herrero, S. Gómez-Ruiz, J. Z. Dávalos, E. Hey-Hawkins, C. R.
- The versatile reactivity of tetra-tert-butyl-cyclopentaphosphanide monoanions. New J. Chem. 34 (2010) 1525-1532
S. Gómez-Ruiz, E. Hey-Hawkins
- Making and breaking of P–P bonds with low-valent transition metal complexes. Europ. J. Inorg. Chem. (2011) 739-747
S. Gómez-Ruiz, R. Frank, B. Gallego, S. Zahn, B. Kirchner, E. Hey-Hawkins
- The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions. Coord. Chem. Rev. 255 (2011) 1360-1386
S. Gómez-Ruiz, E. Hey-Hawkins
- Synthesis and Thermolysis of the Phosphorus-rich Manganese(I) Complex [Mn2(µ- Br){cyclo-(P4But3)PBut}(CO)6]: From Complexes to Metal Phosphides. ChemPlusChem 77 (2012) 341-344
A. Kircali, R. Frank, S. Gómez-Ruiz, B. Kirchner, E. Hey-Hawkins
(See online at https://doi.org/10.1002/cplu.201200013) - One-step routes for the preparation of MPHMes salts from MesPCl2 (M = Li, Na, K; Mes = 2,4,6-Me3C6H2). Inorg. Chem. 52 (2013) 4488-4493
I. Jevtovikj, R. Herrero, S. Gómez-Ruiz, P. Lönnecke, E. Hey-Hawkins
