Nickelacarborane-Supported Bis- N-heterocyclic Carbenes

Runxia Nan; Yiwen Li; Zhouli Zhu; Fan Qi; Xu-Qiong Xiao

doi:10.1021/jacs.3c04360

Nickelacarborane-Supported Bis- N-heterocyclic Carbenes

J Am Chem Soc. 2023 Jul 19;145(28):15538-15546. doi: 10.1021/jacs.3c04360. Epub 2023 Jul 6.

Authors

Runxia Nan^{1

2}, Yiwen Li^{1

2}, Zhouli Zhu^{1

2}, Fan Qi^{1

2}, Xu-Qiong Xiao^{1

2}

Affiliations

¹ College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, No. 2318, Yuhangtang Road, Hangzhou 311121, Zhejiang China.
² Key Laboratory of Silicone Materials Technology of Zhejiang Province, Hangzhou Normal University, No. 2318, Yuhangtang Road, Hangzhou 311121, Zhejiang China.

PMID: 37413790
DOI: 10.1021/jacs.3c04360

Abstract

Metallacarboranes have attracted significant attention due to their unique properties. Considerable efforts have been made on the reactions around the metal centers or the metal ion itself, while transformations of functional groups of the metallacarboranes have been much less explored. We presented here the formation of imidazolium-functionalized nickelacarboranes (2), their subsequent conversion to nickelacarborane-supported N-heterocyclic carbenoids (NHCs, 3), and the reactivities of 3 toward Au(PPh₃)Cl and Se powder, which resulted in the formation of bis-gold carbene complexes (4) and NHC selenium adducts (5). Cyclic voltammetry of 4 shows two reversible peaks, corresponding to the interconversion transformations Ni^II ↔ Ni^III and Ni^III ↔ Ni^IV. Theoretical calculations demonstrated relatively high-lying lone-pair orbitals, weak B-H···H-C interactions between the BH units and the methyl group, and weak B-H···π interactions between the BH groups and the vacant p-orbital of the carbene.