A 12-Vertex Metallacarborane of Silver(I)

• DOI: 10.1021/acs.inorgchem.3c04329
• Publication Date: 2024-03-06T14:49:55Z
• Authors: Beining Wang; Zhouli Zhu; Mei-Juan Liang; Yun-Kang Ren; Jin-Bian Xue; Jia-Ying Zhang; Fan Qi; Xu-Qiong Xiao

The discovery of ferrocene in 1951 was a significant landmark in the field of organometallic chemistry, and since then, numerous sandwich- or half-sandwich metallic complexes have been reported. However, silver stands as an intriguing exception in this regard, and knowledge of its bonding situation has remained undisclosed. Herein, unprecedented 12-vertex metallacarboranes of Ag(I) (2a and 2b) were synthesized through the reaction of sodium hexamethyldisilazide (NaHMDS) with the mixture of nido-C2B9 carborane anion-supported N-heterocyclic carbene precursors (1a and 1b) and [Ag(PPh3)Cl]4. The X-ray structural analysis of the resulting metallacarboranes revealed a unique "slipped" half-sandwich structure, which is a rarity among cyclopentadienyl analogues. DFT calculations provided insights into the asymmetric π-interactions between the pentagonal C2B3 face and the silver ion.