Iridium-mediated regioselective B-H/C-H activation of carborane cage: a facile synthetic route to metallacycles with a carborane backbone.
One-pot reactions of carborane carboxylic acids (L), [Cp*IrCl2]2, and silver salt are reported, which lead to regioselective B-H or C-H bond activation at ambient temperature in good yields. This process is demonstrated for three carborane (o-, m-, p-) dicarboxylates, and metal-mediated B-H functionalization of a p-carborane derivative is accomplished for the first time. Two metal-induced self-assembly routes to tetra-nuclear metallacycles 3 and 5 were performed through B(4, 7)/H and B(2, 10)/H activation, respectively, and the two metallacycles were found to be stable and to exist in solution as discrete complexes. Different activation modes in the carborane cage were ascribed to the characteristic structure of the products and the electronic density differences. The analogous reaction of o-carborane monocarboxylate with the same metal precursor gave the C-H activation complex 6, indicating that the B-H bond is more stable than the C-H bond in this carborane cage. The selective activation was confirmed by DFT calculation results. In this study, a facile and efficient synthetic route has been developed through specific B-H bond activation to construct carborane-based metallacycles that are unavailable by conventional methods.
Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University , Shanghai 200433, P. R. China.
Zi-Jian
ZJ
Yao
Wei-Bin
WB
Yu
Yue-Jian
YJ
Lin
Sheng-Li
SL
Huang
Zhen-Hua
ZH
Li
Guo-Xin
GX
Jin