Castro Castro Paula, Gabbaï François P
Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States.
Organometallics. 2024 Sep 26;43(19):2334-2341. doi: 10.1021/acs.organomet.4c00347. eCollection 2024 Oct 14.
Our interest in the design of ambiphilic ligands and their coordination to gold has led us to synthesize an indazol-3-ylidene gold chloride complex functionalized at the 4-position of the indazole backbone by a stibine functionality. The antimony center of this new complex cleanly reacts with -chloranil to afford the corresponding stiborane derivative. Structural analysis indicates that the stiborane coordination environment is best described as a distorted square pyramid whose open face is oriented toward the gold center, allowing for the formation of a long donor-acceptor, or pnictogen, Au → Sb bonding interaction. The presence of this interaction, which has been probed computationally, is also manifested in the enhanced catalytic activity of this complex in the cyclization of -propargyl-4-fluorobenzamide.
我们对双亲性配体的设计及其与金的配位作用的兴趣，促使我们合成了一种在吲唑主链的4位通过锑功能团官能化的吲唑-3-亚基氯化金配合物。这种新配合物的锑中心与四氯苯醌顺利反应，得到相应的锑硼烷衍生物。结构分析表明，锑硼烷的配位环境最好描述为一个扭曲的四方锥，其开口面朝向金中心，从而能够形成一个长程的供体-受体或氮族元素的Au→Sb键相互作用。这种相互作用的存在已通过计算进行了探究，它也体现在该配合物在炔丙基-4-氟苯甲酰胺环化反应中增强的催化活性上。
