Revisiting Ir(CO)3Cl

Abstract

We return to an old puzzlethe short metal-metal separation and electrical conductivity of the apparently unoxidized one-dimensionally stacked structure of a d 8 Ir(I) complex, Ir(CO) 3 Cl. One would expect neither a short Ir-Ir distance of 2.84 Å, nor metallicity in an unoxidized stacked square-planar d 8 array. We build up dimer, trimer, one-dimensional polymer and model 3-dimensional structures, in both molecular and extended structure plane wave calculations. The short Ir-Ir separation in the polymer, with a substantial contribution of 6p z -5d z2 bonding to it, is obtained without any oxidation. There is computational evidence for an important level crossing in the polymer. The metallicity remains unexplained, but likely arises from partial oxidation. And that remains an outstanding experimental issue. ] G. A. Landrum, YAeHMOP: Yet Another extended Hückel Molecular Orbital Package, Version 3.0; http://sourceforge.net/projects/yaehmop/. *Graphical Abstract -Pictogram (for review)One would expect neither a short Ir-Ir distance of 2.84 Å, nor metallicity in an unoxidized stacked square-planar d 8 array, as one sees in the structure of Ir(CO) 3 Cl. In calculations, a short Ir-Ir separation is obtained and explained, without any oxidation. The metallicity remains a puzzle. *Graphical Abstract -Synopsis (for review)

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