Yu Cheng-Han, Au-Yeung Ka-Chun, Liu Ruiqin, Lee Chao-Hsien, Jiang Dandan, Semagne Aweke Bamlaku, Wu Chia-Hung, Wang Yu-Jou, Wang Ting-Hsuan, Voon Kong Kien, Yap Glenn P A, Chen Wen-Ching, Frenking Gernot, Zhao Lili, Ong Tiow-Gan
Institute of chemistry, Academia Sinica, Taipei, Taiwan (R.O.C., 115201.
Corporate R&D Center, LCY Chemical Corporation, Kaohsiung, Taiwan (R.O.C.
Chemistry. 2023 Dec 19;29(71):e202302886. doi: 10.1002/chem.202302886. Epub 2023 Nov 6.
Carbodicarbene (CDC) has become an emerging ligand in many fields due to its strong σ-donating ability. <We report the first synthesis of the anionic CDC Pd complexes containing a BF moiety within the framework to leverage the electronic feature of carbon carbone. The elucidation of X-ray crystal structures, ligand competition as well as transmetallation experiments suggest that the anionic moiety has enhanced the overall donor strength of the traditional neutral CDC. Importantly, this anionic scaffold exhibits a facile second coordination toward Au(I), Ag(I) and Pd(II) without any external ligand assistance, whereas previously reported neutral pincer CDC complexes do not possess a two-fold donor capacity. The analysis of the bonding situation via theoretical methods shows that the description of the anionic CDC moieties in terms of dative bonding is preferred over the model of delocalized positive charge, as it accounts for the two-fold donor ability of the divalent carbon atom, preserving a characteristic feature of a carbone.
由于其强大的σ供体能力，碳二卡宾（CDC）已成为许多领域中新兴的配体。<我们首次合成了在框架内含有BF部分的阴离子CDC钯配合物，以利用碳碳的电子特性。X射线晶体结构的阐明、配体竞争以及转金属化实验表明，阴离子部分增强了传统中性CDC的整体供体强度。重要的是，这种阴离子支架在没有任何外部配体协助的情况下，对Au（I）、Ag（I）和Pd（II）表现出容易的二次配位，而先前报道的中性钳形CDC配合物不具备双重供体能力。通过理论方法对键合情况的分析表明，用配位键描述阴离子CDC部分比离域正电荷模型更可取，因为它解释了二价碳原子的双重供体能力，保留了碳烯的一个特征。
