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Published on: June 19, 2015
Facile reactions of gold(i) complexes with tri(tert-butyl)azadiboriridine
Rong Shang1, Souta Saito, J Oscar C Jimenez-Halla
1Department of the Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, 7398526 Higashi-Hiroshima, Japan. rshang@hiroshima-u.ac.jp.
Abstract:
Direct structural evidence for group 11 metal-mediated B-B bond activation was obtained from reactions of tri(tert-butyl)azadiboriridine (1) with AuCl(L) complexes. The AuCl(SMe2) reaction afforded [η2-B,B-B(tBu)N(tBu)B(tBu)]AuCl (2) by ligand displacement. More donating phosphines as co-ligands led to B-B bond cleavage accompanied by either halide or L migration to form boron-gold complexes 3 (L = PPh3) and 4 (L = PMe3). A similar product 5, which is isostructural to 4, was obtained by the addition of dimethylaminopyridine (DMAP) to 2-4. Complexes 2-5 constitute rare examples of metal complexes bearing two Lewis acidic centres. The effect of the boryl ligand was demonstrated in the formation of a gold(i) complex 6 bearing a 5-membered heterocycle from 3 and tert-butylisonitrile. Plausible reaction mechanisms that led to these complexes and their bonding situation were explored computationally at the DFT level.
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