Ulf Vogel

Lewis-Säure/Base-stabilisiertes Phosphanylalan und -gallan

Weder synthetisiert noch in Matrix nachgewiesen wurden bislang die Stammverbindungen des Phosphanylalans bzw. -gallans vom Typ A. Durch H2-Eliminierungsreaktionen zwischen [(CO)5WPH3] und H3ENMe3 (E=Al, Ga) konnten nunmehr erstmals Lewis-Saure/Base-stabilisierte Komplexe des Typs B synthetisiert werden. Umfassende Dichtefunktionalrechnungen an den Aluminiumverbindungen belegen die hohe Stabilitat der Komplexe vom Typ B.

Complex Chemical Stabilization of Dichlorodiphosphene

In contrast to the cis configuration of N2 F2 , the analogous phosphorus subhalogenides, P2 X2 (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.

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. Compounds 2 and 3 are the first of a new class of Group 13/15 compounds which show no additionally donor-acceptor bonds within the framework.

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. DFT calculations predict that hydrogen elimination in the case of [({(CO)(5)W}PhPAlH⋅NMe(3))(2)] may be reversible.

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.

Synthesis of Novel Transition Metal-Group 15 Cage Compounds and their Use as Molecular Precursors for Binary and Ternary Transition Metal Pnictides

The reaction of [{W(CO)5}2PCl] with K[Co(CO)4] yields the novel compounds [W(CO)4(η4-〈Co(CO)3P{W(CO)5}〉2)[ (1) and [{(CO)4WCo3(CO)6}(μ3-P{W(CO)5})] (2) along with the previously known derivatives [Co2(CO)6(μ,η2-P2{W(CO)5}2)] (3) and [Co3(CO)9(μ3-P{W(CO)5})] (4). Complex [W2(CO)8(μ-CO)(μ,η2-P2{W(CO)5}2) (5) was synthesised by reacting Na2[W2(CO)10] with PBr3. Reaction of K[Mn(CO)5] with SbCl3 affords [Sb{Mn(CO)5}3] (6) in high yields. Furthermore, the thermogravimetric analysis of 1, 4, 5 and 6 is discussed.