A (μ-hydrido)diborane(4) anion and its coordination chemistry with coinage metals. Issue 10 (23rd February 2022)

• Record Type: Journal Article
• Authors: Mao, Xiaofeng; Zhang, Jie; Lu, Zhenpin; Xie, Zuowei
• Is Part Of: Chemical science. Volume 13:Issue 10(2022)
• Page Start: 3009
• Page End: 3013
• Publication Date: 2022-02-23
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc00318j
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : A tetra( o -tolyl)(μ-hydrido)diborane(4) anion is facilely prepared via the reaction of tetra( o -tolyl)diborane(4) with NaH. It exhibits a σ-B–B bond nucleophilicity towards NHC-metal halides to give the corresponding η 2 -B–B bonded metal complexes. Abstract : A tetra( o -tolyl) (μ-hydrido)diborane(4) anion 1, an analogue of [B2 H5 ] − 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.