A (μ-hydrido)diborane(4) anion and its coordination chemistry with coinage metals.
Xiaofeng MaoJie ZhangZhenpin LuZuowei XiePublished in: Chemical science (2022)
A tetra( o -tolyl) (μ-hydrido)diborane(4) anion 1, an analogue of [B 2 H 5 ] - species, was facilely prepared through the reaction of tetra( o -tolyl)diborane(4) with sodium hydride. Unlike common sp 2 -sp 3 diborane species, 1 exhibited a σ-B-B bond nucleophilicity towards NHC-coordinated transition-metal (Cu, Ag, and Au) halides, resulting in the formation of η 2 -B-B bonded complexes 2 as confirmed by single-crystal X-ray analyses. Compared with 1, the structural data of 2 imply significant elongations of B-B bonds, following the order Au > Cu > Ag. DFT studies show that the diboron ligand interacts with the coinage metal through a three-center-two-electron B-M-B bonding mode. The fact that the B-B bond of the gold complex is much prolonged than the related Cu and Ag compounds might be ascribed to the superior electrophilicity of the gold atom.
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