Peter W. Roesky

The reaction of N,N′-bis(4-carboxysalicylidene)ethylenediamine featuring carboxylate groups in the meta position to the OH groups, with nickel and copper acetate in the presence of a base, results in metal-functionalized, two-dimensional coordination polymers.

Diethylzinc and dimethylanilinium tetrakis(pentafluorophenyl)borate were found to catalyze hydroaminations at room temperature in high efficiency and very short reaction times. The reactivity of the proposed cationic zinc species, which is assumed to catalyze the reaction, strongly depends on the coordinative abilities of the counterion.

Bis(phosphinimino)methanides exhibit a wide variety of coordination chemistry with almost all elements in the periodic table. This critical review deals with the chemistry and coordination behavior of bulky monoanionic {CH(PPh₂NR)₂}⁻ bis(phosphinimino)methanide and dianionic {C(PPh₂NR)₂}²⁻ bis(phosphinimino)methanediide (R = SiMe₃, aryl) ligands focusing on s- and p-block as well as transition metals (109 references).

Depending on the ionic radius of the central metal atom the BH₄ ⁻group, which usually reacts in lanthanide chemistry like a pseudo halide, can be involved in redox chemistry and the resulting product contains an N–BH₃ unit, which binds in an unusual η²-fashion onto the metal atom.

Excellent couplings: Recent developments in the metal‐catalyzed CH activation of sp³ centers in an α position relative to an amine nitrogen atom are presented. Their reaction with alkenes to give alkylamines (hydroaminoalkylation) is also summarized (see general scheme). magnified image

Exzellente Kupplungen: In letzter Zeit waren einige spannende Entwicklungen bei der metallkatalysierten C‐H‐Aktivierung von sp³‐Zentren in α‐Position zu einem Aminstickstoffatom und ihren Reaktionen mit Alkenen zu Alkylaminen (Hydroaminoalkylierung) zu verzeichnen (siehe allgemeines Schema), die in diesem Highlight zusammengefasst werden. magnified image

Two new bis(phosphinimino)methanide complexes of divalent ytterbium, [{(Me₃SiNPPh₂)₂CH}₂Yb], and strontium, [{(Me₃SiNPPh₂)₂CH}₂Sr], were synthesized from the corresponding metal diiodides and of K{CH(PPh₂NSiMe₃)₂}. Alternatively, the ytterbium compound could also be obtained starting from [{(Me₃SiNPPh₂)₂CH}YbI(THF)₂]. A comparison of the properties with the analogues compounds [{(Me₃SiNPPh₂)₂CH}₂M] (M = Ca, Ba, Sm, Eu) is given.

[{(η⁵-C₅Me₅)₂Sm}₄P₈], a molecular polyphosphide of the rare-earth elements having a realgar core structure, was synthesized by a one-electron redox reaction of divalent samarocen and white phosphorus.

The application of low-valent group 13 metal compounds as ligands in coordination chemistry results in the formation of new metal-to-metal bonds. Traditionally, the coordination chemistry of these compounds was focused on late transition metals. This article now reviews recent progress of the coordination chemistry of compounds with low-valent group 13 metals in the chemistry of electron poor main group and transition metal as well as in f-block elements.