Andrada Diego M, Holzmann Nicole, Hamadi Thomas, Frenking Gernot
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, D-35032 Marburg, Germany.
Laboratoire International Associé Centre National de la Recherche Scientifique - UMR 7565, Université de Lorraine, 54506 Vandoeuvre-lès-Nancy, France.
Beilstein J Org Chem. 2015 Dec 24;11:2727-36. doi: 10.3762/bjoc.11.294. eCollection 2015.
Fifteen cyclic and acylic carbenes have been calculated with density functional theory at the BP86/def2-TZVPP level. The strength of the internal X→p(π) π-donation of heteroatoms and carbon which are bonded to the C(II) atom is estimated with the help of NBO calculations and with an energy decomposition analysis. The investigated molecules include N-heterocyclic carbenes (NHCs), the cyclic alkyl(amino)carbene (cAAC), mesoionic carbenes and ylide-stabilized carbenes. The bonding analysis suggests that the carbene centre in cAAC and in diamidocarbene have the weakest X→p(π) π-donation while mesoionic carbenes possess the strongest π-donation.
已采用密度泛函理论在BP86/def2-TZVPP水平上对15种环状和非环状卡宾进行了计算。借助自然键轨道（NBO）计算和能量分解分析，估算了与C（II）原子相连的杂原子和碳的内部X→p（π）π-给体强度。所研究的分子包括氮杂环卡宾（NHC）、环状烷基（氨基）卡宾（cAAC）、中氮茚卡宾和叶立德稳定卡宾。键合分析表明，cAAC和二氨基卡宾中的卡宾中心具有最弱的X→p（π）π-给体，而中氮茚卡宾具有最强的π-给体。
