Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543.
Inorg Chem. 2020 Jun 15;59(12):8451-8460. doi: 10.1021/acs.inorgchem.0c00886. Epub 2020 Jun 2.
A library of 14 heterobis(carbene) complexes of the general formula [Au(Pr-bimy)(ADC)]BF (-) containing the N-heterocyclic carbene reporter Pr-bimy and various protic acyclic diaminocarbenes (ADCs) have been prepared to estimate their stereoelectronic properties by C NMR spectroscopy and percentage buried volume (%) determinations. Their preparation was achieved by nucleophilic attack of five secondary amines on six mixed NHC/isocyanide complexes of the type [Au(Pr-bimy)(CN-R)]BF (-). Analyses of the Pr-bimy carbene signals reveal that protic ADCs are stronger donors than classical and expanded-ring NHCs. On the other hand, they are weaker donating compared to NHCs with reduced-heteroatom stabilization. Moreover, stereoelectronic fine-tuning of these ligands is possible by a diverse range of substituents originating from the employed isocyanides and amines.
已制备出包含 N-杂环卡宾报告者 Pr-bimy 和各种质子非环二胺碳烯 (ADCs) 的 14 种通用式 [Au(Pr-bimy)(ADC)]BF (-) 的杂双(卡宾)配合物库，通过 C NMR 光谱和百分比埋置体积 (%) 测定来估计它们的立体电子性质。它们的制备是通过将五个仲胺亲核攻击六种混合 NHC/异氰化物配合物 [Au(Pr-bimy)(CN-R)]BF (-) 来实现的。对 Pr-bimy 卡宾信号的分析表明，质子 ADC 比经典和扩展环 NHC 更强的供体。另一方面，与具有降低杂原子稳定化的 NHC 相比，它们的供电子能力较弱。此外，通过从所使用的异氰化物和胺衍生出的各种取代基，可以对这些配体进行立体电子微调。
