Insight into the formation of bismuth-tungsten carbonyl clusters.

Multimetallic clusters play a key role as models to doped metals, as candidates to new types of superatomic catalysts and as precursors to new multimetallic solids. Understanding formation pathways is an essential and necessary step forward in the development of cluster synthesis and research, yet remains considerably lacking owing to difficulty in identification of intermediates and the ill-defined nature of common starting materials. Here we show progress in this regard by investigating the reactivity of an intermetallic solid of nominal composition 'KGaBi' with [W(cod)(CO)] upon extraction with ethane-1,2-diamine (en) and 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.

Between Elemental Match and Mismatch: From K Ge Sb to Salts of (Ge Sb ) , (Ge Sb ) , and (Ge Sb ).

The solid mixture "K GeSb" was shown to comprise single-crystalline K Ge Sb (1), a double salt of K [GeSb ] with carbonate-like [GeSb ] anions, and the metallic Zintl phase K Ge . Extraction of 1 with ethane-1,2-diamine in the presence of crypt-222 afforded [K(crypt-222)] salts of several novel binary Zintl anions: (Ge Sb ) (in 2), (Ge Sb ) (in 3), and in the presence of [AuMePPh ] also (Ge Sb ) (in 4). The anion in 2 represents a predicted, yet heretofore missing pseudo-tetrahedral anion.

[M@SnSb] (M = La, Ce, or U; = 6-8; = 3, 4): Interaction of 4f or 5f Metal Ions with 5p Metal Atoms in Intermetalloid Clusters.

The impact of 4f metal ions Ln (Ln = La or Ce) versus 5f metal ions U ( = 3 or 4) on the compositions and distribution of 5p metal atoms in the cluster shells of endohedral species [M@SnSb] (M = La, Ce, or U; = 6-8; = 3, 4) was studied by means of combined experimental and quantum chemical investigations. While all known f-block metal ion-centered endohedral clusters possessed combinations of larger main group metal atoms so far (Sn/Bi or Pb/Bi), resulting in mixtures of 13- and 14-atom cages, the 14-atom cages reported herein comprise exclusively Sn and Sb atoms and therefore are challenged in accommodating the large 4f and 5f ions. We show that the clusters form in reactions of (SnSb) anions with [Ln(CMeH)] or [U(CMeH)Cl], and that salts of [La@SnSb], [La@SnSb], [U@SnSb], and [U@SnSb] can be isolated from them.

High-Spin Imido Cobalt Complexes with Imidyl Radical Character*.

We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L ] , (L=N(Dipp)SiMe ), Dipp=2,6-diisopropylphenyl) with very long Co-N bonds of around 1.75 Å. Their electronic structure was interrogated using a variety of physical and spectroscopic methods such as EPR or X-Ray absorption spectroscopy which leads to their description as highly unusual imidyl cobalt complexes.