De Las Nieves Piña María, Burguera Sergi, Buils Jordi, Àngel Crespí Miquel, Ernesto Morales Julian, Pons Jordi, Bauzá Antonio, Frontera Antonio
Departament de Química, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122, Palma de Mallorca (Baleares), Spain.
Chemphyschem. 2022 Apr 20;23(8):e202200010. doi: 10.1002/cphc.202200010. Epub 2022 Mar 8.
Long range substituent effects in regium bonding interactions involving Au(I) linear complexes are investigated for the first time. The Au(I) atom is coordinated to two para-substituted pyridine ligands. The interaction energy (RI-MP2/def2-TZVP level of theory) of the π-hole regium bonding assemblies is affected by the pyridine substitution. The Hammett's plot representations for several sets of Lewis bases have been carried out and, in all cases, good regression plots have been obtained (interaction energies vs. Hammett's σ parameter). The Bader's theory of "atoms-in-molecules" has been used to evidence that the electron density computed at the bond critical point that connects the Au-atom to the electron donor can be used as a measure of bond order in regium bonding. Several X-ray structures retrieved from the Cambridge Structural Database (CSD) provide experimental support to the existence of π-hole regium bonding in [Au(Py) ] derivatives.
首次研究了涉及金（I）线性配合物的区域键合相互作用中的远程取代基效应。金（I）原子与两个对位取代的吡啶配体配位。π-空穴区域键合组装体的相互作用能（理论水平为RI-MP2/def2-TZVP）受吡啶取代的影响。已经对几组路易斯碱进行了哈米特图表示，并且在所有情况下，都获得了良好的回归图（相互作用能与哈米特σ参数）。“分子中的原子”的巴德理论已被用于证明在连接金原子与电子供体的键临界点处计算的电子密度可作为区域键合中键级的量度。从剑桥结构数据库（CSD）检索到的几个X射线结构为[Au(Py)]衍生物中π-空穴区域键合的存在提供了实验支持。
