Coordination Behavior of [Cp'' Zr(η -P )] towards Different Lewis Acids.

A detailed method for the preparation of [Cp'' Zr(η -P )] (1) is presented. The coordination behavior of 1 towards Lewis acidic transition metal complexes of tungsten, manganese, and iron, respectively, and main group compounds (AlMe , AlEt ) was investigated in detail by computational and experimental studies. In doing so, a series of unprecedented complexes with different coordination modes and multiple coordination numbers of the tetraphosphabicyclo[1.

Selective dimerization of Lewis-acid/base-stabilized phosphanylalanes.

The reaction of [{(CO)(5)W}PRH(2)] (R = H, Ph) with H(3)Al⋅NR(3) (R = Et, Me) leads to the formation of four-membered heterocyclic compounds [({(CO)(5)W}P(H)AlH⋅NEt(3))(2)] and [({(CO)(5)W}PhPAlH⋅NMe(3))(2)]. Upon dissolving the solid compounds, fast equilibria between the isomers are observed on the NMR timescale. Further insight into the stability and reactivity of the isomers was gained by applying theoretical methods.

Controlled oligomerization of Lewis acid/base-stabilized phosphanylalanes.

PAls should stick together: The cyclo-trimer 2 is obtained by H(2) elimination of Lewis acid/base-stabilized parent compound of the phosphanylalanes 1. The elimination is controlled by fine tuning the temperature and solvent conditions. A subsequent H(2) elimination produces the ladder compound 3.

Copper(I) mediated oligomerisation of a phosphaalkyne.

The oligomerisation of tert-butylphosphaalkyne, tBuC[triple bond, length as m-dash]P, mediated by Cu(I) complexes yields an unprecedented C4P5 cage compound, which is stabilised in a matrix of copper(I) iodide.

The surprising and stereoselective formation of P2C10 cages by the reduction of Cp*PCl2.

Reactions of Cp*PCl2 with Group 13 reducing agents result in a cascade of P-C, P-P and C-C bond forming reactions and the stereoselective formation of P2C10 cages.

The stabilization of monomeric parent compounds of phosphanyl- and arsanylboranes.

The structures of the parent compounds of phosphanyl- and arsanylboranes, H(2)BPH(2) and H(2)BAsH(2), were calculated by DFT-B3LYP methods. Such compounds have not previously been obtained preparatively. By applying the concept of Lewis acid/base stabilisation, [(CO)(5)W(H(2)EBH(2).

Complex Chemical Stabilization of Dichlorodiphosphene.

In contrast to the cis configuration of N F , the analogous phosphorus subhalogenides, P X (X=F, Cl) adopt a trans configuration according to density functional theory calculations. Now for the first time dichlorodiphosphene has been stabilized in the coordination sphere of transition metals in the form of complex 1.