Abstract
In this contribution, we studied the OC-C bond in carbon suboxide and related allene compounds using the valence bond method. The nature of this bond has been the subject of debate, whether it is a regular, electron sharing bond or a dative bond. We compared the nature of this bond in carbon suboxide with the gold-CO bond in Au(CO)2+, which is a typical dative bond, and we studied its charge-shift bond character. We found that the C-CO bond in carbon suboxide is unique in the sense that it cannot be assigned as either a dative or electron sharing bond, but it is an admixture of electron sharing and dative components, together with a high contribution of ionic character. These findings provide a clear basis for distinguishing the commonly found dative bonds between ligands and transition metals and the present case of what may be described as coordinative bonding to carbon.
| Original language | English |
|---|---|
| Pages (from-to) | 3327-3334 |
| Number of pages | 8 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 23 |
| Issue number | 5 |
| DOIs | |
| State | Published - Feb 7 2021 |
Funding
This research used resources (Summit and SummitDev) of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725 (DD and ESP). This work was sponsored by NWO Exact and Natural Sciences for the use of supercomputer facilities (contract no. 17197 7095). We would like to thank the Center for Information Technology of the University of Gronin-gen for their support and for providing access to the Peregrine high performance computing cluster. J. E. M. N. K. acknowledges funding from the Netherlands Organisation for Scientific Research (NWO START-UP grant (740.018.014)).