The enhanced electron-donor properties of the bulky bisimino ligand 1,2-(L N) -C H (1; L =1,3-bis(mesityl)-imidazolin-2-ylidene), mesityl=2,4,6-trimethylphenyl) were exploited for the stabilization of elusive electron-deficient and low-coordinate boron dication species. The reaction of 1 with PhBBr or (B(Cl)NMe ) afforded a dicationic mononuclear boron(III) complex or a dicationic dinuclear boron(II) complex, respectively (4 , 6 ). The bonding situations of 4 and 6 were examined by means of single crystal X-ray diffraction analysis, as well as theoretical methods. Significant allocation of positive charge density into the ligand system was diagnosed for both dications. However, the metalloid-centered Lewis acidity of the dications was confirmed via hydride transfer reactions.
The 1 : 4 and 1 : 2 complexes of silver perrhenate and triphenylphosphine, [(Ph3P)4Ag](+) ReO4(-) and [(Ph3P)2AgReO4]2, have been prepared and their structures determined in the solid state by X-ray diffraction. The former is composed of independent ions, while in the latter the ions are aggregated into cyclic dimers. The silver centers are tetracoordinated including contact with two bridging perrhenate anions, setting this structure apart from that of its gold analogue [(Ph3P)2Au](+) ReO4(-) where the gold centers are strictly two-coordinate.
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