Asymmetrical Platinum and Rhodium Dinuclear Complex Strongly Bound to Filled d_z2 Complexes by Unbridged Pt-Metal Bonds: Toward Heterometallic-Extended Metal Atom Chains

Heterometallic extended metal atom chains (EMACs) aligned with three types of metal were rationally synthesized by forming unbridged metal-metal bonds based on the interactions between highest occupied and lowest unoccupied molecular orbitals at the dz2 orbital. These chains form pentanuclear structures aligned as Rh -Pt -M -Pt -Rh with relatively large formation constants of 5.0x 10(13 )M(-2) for M= Pt and 6.3 x10(11) M-2 for M =Pd, while retaining their back -bones in solution. In the case of M=Cu, the original Cu(+2) atoms were reduced to Cu(+ 1) during the synthetic process. Cu(+1) has an unprecedented trigonal bipyramidal coordina-tion geometry. The reported synthesis based on asymmetrical dinuclear complexes provides a guideline for the synthesis of hetero-EMACs to allow several analogs through judicious combinations realized by tuning the number of metal nuclei and metal species.