Metallophilic bonding in heterometallic complexes has attracted the attention of chemists over the past several decades due to their unique structural, spectroscopic, and photophysical properties that cannot only be attributed to the nature of the coordinated ligands. In addition, theoreticians and experimentalists have extensively investigated intramolecular d10-d10 interactions in hetero- and homometallic polynuclear structures. Our theoretical study contribution is focused on efforts to prove a new short genuine M-M bonds and estimate the M-M’ bond energy in such (PH3Cl)2MM’ complexes (where M or M' = Ag, Au and Cu) using quantum mechanical calculations within DFT, ab initio and EHT methods. Optimization of geometry gives there different structures: staggered, gauche, and double-bridged (with an -M-Cl-M’-Cl- four-membered ring) exhibits substantial difference in term of d10-d10 bonds. It comes from the attractive effect in such heterobimetallic bonds which show a drastically shortened MM’ bond typically coming from the mixing (n+1)s and (n+1)p orbitals of M with the (n)d’ orbitals of M’. A potential well minimum was located at the HF level, opposite to the behavior reported by Pyykko for Au-Au complexes, suggesting at least partial covalent bonding in such (PH3Cl)2MM’ complexes. EHT calculations underscore the existence of the aforementioned sd’/pd’ orbital mixing even more drastically than what was reported by Hoffmann for Cu-Cu complexes, as surmised by overlap population and fragment diagram interactions. Under various theoretical treatments, equilibrium Cu-Au bond distances as short as 2.500 Å for the staggered conformer, and 2.54 Å for the gauche conformer, and 2.72 Å for the double-bridged isomer in their singlet ground state. Experimentally, different attempts of crystallization are under investigation in multiple classes of M-M’ species with different ligands following the original discovery of the phenomenon.

Computational studies of d10-d10 metal-metal bonds in (PH3Cl)2MM’ with (M and M’ =Cu, Ag, Au) and other heterobimetallic complexes: Description of bona fide M-M’ Bonds

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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