From phosphanylphosphaalkenes to coordination copper and silver polymers containing P-P bonds.

This study was focused on the activation of the CP bond via reactions of Ph2CP-PtBu2 (1) with 1,6-hexanediol and selected dithiols (1,4-butanedithiol, 1,4-benzenedithiol and 1,4-benzenedimethanethiol). These reactions proceed according to a 1,2-addition mechanism, providing new compounds with formulas {(Ph)2(H)C-P-PtBu2}{µ2-(O-(CH2)6-O)}{tBu2P-P-C(H)(Ph)2} (2), {(Ph)2(H)C-P-PtBu2}{µ2-(S-(CH2)4-S)}{tBu2P-P-C(H)(Ph)2} (3a), {(Ph)2(H)C-P-PtBu2}{µ2-(S-C6H4-S)}{tBu2P-P-C(H)(Ph)2} (3b), and {(Ph)2(H)C-P-PtBu2}{µ2-(S-CH2-C6H4-CH2-S)}{tBu2P-P-C(H)(Ph)2} (3c). Next, the reactions of 3a and 3c with metal chlorides led to the growth of desired coordination polymers of copper(I) and silver(I). All the obtained compounds remained stable under atmospheric conditions.

Magnesium(I) Halide versus Magnesium Metal: Differences in Reaction Energy and Reactivity Monitored in Reduction Processes of P-Cl Bonds.

Magnesium(I) halides (MgI X; X=Cl, Br, I), as high temperature molecules, are trapped and finally stored at -80 °C in toluene/donor solutions. These solutions provide insights into the fundamental mechanism of reduction reactions using activated magnesium metal as a prototype for every base metal. The most important example of such a reaction is the preparation of Grignard reagents (RMgX). The details of this highly complex mechanism especially of intermediates between Mg metal and MgII (RMgX) remain unknown until today. The same is true for the reaction of bulk magnesium with Group 15 halide compounds that give biradicaloid species. We investigate the reduction of P-Cl bonds with solutions of [MgI Br(Nn Bu3 )]2 (1). The phosphanes [ClP(µ-NTer)]2 (2) and (Me3 Si)2 N-PCl2 (3), were chosen as they had successfully been reduced by Mg metal before. Furthermore, reactions of both 1 and Mg metal are compared with an MgI chelate complex L1 Mg-MgL1 containing a strong Mg-Mg σ-bond.

Hunting for the magnesium(I) species: formation, structure, and reactivity of some donor-free Grignard compounds.

Magnesium bromide radicals have to be prepared as high-temperature molecules and trapped as a metastable solution because a seemingly simple reduction of donor-free Grignard compounds failed. However, the essential role of magnesium(I) species during the formation of Grignard compounds could be demonstrated experimentally.

Trichloridobis(ethyl-diphenyl-phosphine)(tetra-hydro-furan)-molybdenum(III).

In the mononuclear title compound, [MoCl(3)(C(4)H(8)O)(C(14)H(15)P)(2)], obtained by the reaction of trichloro-tris-(tetra-hydro-furan)-molybdenum(III) and ethyl-diphenyl-phosphine in tetra-hydro-furan (THF) solution, the Mo(III) atom is six-coordinated by one O atom of a THF mol-ecule, two P atoms from two ethyl-diphenyl-phosphine ligands and three Cl atoms in a distorted octa-hedral geometry. The C atoms of the THF molecule are disordered over two positions in a 0.55 (2):0.45 (2) ratio.