From alkaline earth to coinage metal carboranyls.

The β-diketiminato calcium and magnesium complexes, [(BDI)Mg n Bu] and [(BDI)CaH] 2 (BDI = HC{C(Me)NDipp} 2 ; Dipp = 2,6-di-isopropylphenyl), react with ortho -carborane ( o -C 2 B 10 H 12 ) to provide the respective [(BDI)Ae( o -C 2 B 10 H 11 )] (Ae = Mg or Ca) complexes. While the lighter group 2 species is a monomer with magnesium in a distorted trigonal planar environment, the heavier analogue displays a puckered geometry at calcium in the solid state due to Ca⋯H-B intermolecular interactions. These secondary contacts are, however, readily disrupted upon addition of THF to provide the 4-coordinate monomer, [(BDI)Ca(THF)( o -C 2 B 10 H 11 )]. [(BDI)Mg( o -C 2 B 10 H 11 )] was reacted with [NHC IPr MCl] (NHC IPr = 1,3-bis(isopropyl)imidazol-2-ylidene; M = Cu, Ag, Au) to provide [NHC IPr M( o -C 2 B 10 H 11 )], rare C -bonded examples of coinage metal derivatives of unsubstituted ( o -C 2 B 10 H 11 ) - and confirming the alkaline earth compounds as viable reagents for the transmetalation of the carboranyl anion.