The approach of two atoms with an unpaired electron each results in the formation of a σ bond. Snapshots of the primary step with a large atom‐to‐atom distance and a parallel spin of both electrons and of the final product, consisting of a butterfly structure with a short AlAl σ bond, have been identified for a [R2PAl(PR2)AlPR2] compound using quantum chemical calculations and X‐ray crystallography (see scheme).
Recently, compounds containing metal-metal bonds between main-group elements have attracted interest to a surprising extent. [1][2][3][4][5] In spite of the latest structural results for two crystalline Mg 2 R 2 compounds (R1 = [ArNC(NiPr 2 )NAr] À ; R2 = [{ArNCMe} 2 CH] À ; Ar= 2,6-diisopropylphenyl, iPr = isopropyl) [2] and in spite of a number of theoretical contributions on molecules with MgÀMg bonds, [10][11][12] several important questions still remain to be answered, for example, concerning the unexpected disproportionation stability of the abovementioned Mg I compounds. Herein, we present the following results: 1) On the basis of quantum-chemical-assisted thermodynamic calculations, a feasible synthesis of radical monomeric Mg I halides at temperatures near 900 8C is presented.2) The nature of the MgÀMg bond is investigated by spectroscopic examination of MgCl and its linear dimer Mg 2 Cl 2 in solid inert-gas matrixes; the MgÀMg dissociation energy is obtained. 3) By comparing the thermodynamics of Mg 2 Cl 2 (1), Mg 2 Cp 2 (2, Cp = cyclopentadienyl), and a model compound Mg 2 R* 2 (3, R* = C(NH 2 )(NCH 3 ) 2 ) analogous to crystalline Mg 2 (R1) 2 , the enormous disproportionation stability of the latter compound is explained. For further investigations, for example in the field of metal-rich Mg n R m clusters (n > m), the synthesis of reactive starting materials like MgCl is absolutely necessary. Initial results on the synthesis of MgCl are reported.After the first evidence for stable alkaline earth
The outstanding position of metalloid clusters as intermediates between the bulk metals and bulk salts on the one hand and of naked metal atom clusters and salt-like clusters on the other hand is described first. Subsequently, a different more chemical description of structure and bonding of a recently published gold-thiolate Au 102 (SR) 44 cluster based on the results of aluminum-/gallium clusters is presented. This comparison shows that there is no principal but only a gradual difference between the Au 102 cluster and the large number of metalloid aluminum-/gallium clusters: both have a metalloid character, i.e. there is a highly mixed valent bonding situation of the metal atoms involved. Therefore these clusters represent a highly complex system and are far from being only nanoscaled metal particles surrounded by a shell of protecting ligands. In detail this comparison shows that the metalloid gold and the aluminum-/gallium clusters are similar in the center, as these metal-metal interactions are energetically similar to those of the
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