Selective dimerization of a trinuclear mixed-metal sandwich complex: construction of an axially chiral metal skeleton.

Certain metal sandwich complexes undergo dimerization through metal-metal bond formation. Here, we found that a reductive dimerization of mixed-metal Pd2Pt or PdPt2 sandwich complexes proceeds through selective Pt-Pt bond formation. A restricted rotation at the Pt-Pt bond of the PdPt2 dimer gave a unique axially chiral structure derived from a heterometal arrangement in a mixed-metal cluster.

Three-Dimensional Sandwich Nanocubes Composed of 13-Atom Palladium Core and Hexakis-Carbocycle Shell.

Coordination of cyclic unsaturated hydrocarbons to transition metal generally gives bis-ligated sandwich complexes, which are a fundamental class of organometallic compounds. This sandwich structure may be extended to a higher-order three-dimensional one when more than two carbocyclic ligands surround an agglomerate of many transition metal atoms. Here, we report synthesis of three-dimensional sandwich nanocube compounds containing a close-packed transition metal cluster core. Reduction of a [Pd3(µ3-C7H7)2]2+ with tetraarylborate under neat conditions afforded [Pd13(µ4-C7H7)6]2+ containing a cuboctahedral Pd13 core with an octahedral ligand-shell.