TY - JOUR
T1 - The electronic structure of carbones revealed
T2 - insights from valence bond theory
AU - Havenith, Remco W. A.
AU - Cunha, Ana V.
AU - Klein, Johannes E. M. N.
AU - Perolari, Francesca
AU - Feng, Xintao
PY - 2021/2/7
Y1 - 2021/2/7
N2 - 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.
AB - 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.
U2 - 10.1039/d0cp05007e
DO - 10.1039/d0cp05007e
M3 - Article
VL - 23
SP - 3327
EP - 3334
JO - PPCP : Physical Chemistry Chemical Physics
JF - PPCP : Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 5
ER -