NHC-Induced Dismutation of Gallium–Zinc Bonds

Journal article

The insertion of gallium­(I) reagent [(BDI)­GaI] (I, BDI = HC­{C­(CH3)­Ndipp}2; dipp = 2,6-di-isopropyl-phenyl) into ZnII–X bonds (X = OTf, Cl) to provide gallyl zinc complexes [(BDI)­Ga­(X)­Zn­(X)­L2] (1 – 3; L2 = thf2, tmeda; tmeda = N, N, N′, N′-tetramethylethylenediamine) is readily reversed by ligand substitution with an N-heterocyclic carbene (NHC), regenerating I and eliminating (NHC) n ZnX2 via ‘dismutation’ of the Ga–Zn bond. The dative Ga→Zn interaction present in [(BDI)­Ga·Zn­(Cl)­(tmeda)]­[BArF 4] (4; ArF = C6H3-3,5-(CF3)2) is similarly disrupted by the addition of NHC. [(BDI)­Ga­(X)­Zn­(X)­L2] complexes also react as a ‘masked’ source of I, as demonstrated by reactions with Et3NHCl and B­(C6F5)3, which yield the respective literature compounds [(BDI)­Ga­(H)­Cl] and [(BDI)­Ga·B­(C6F5)3].

Authors: Morris, LJ; Collins Rice, CG; O’Hare, D

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Chemical Society
• Journal: Organometallics
• Volume: 45
• Issue: 10
• Pages: 1122-1127
• Publication date: 2026-05-13
• Acceptance date: 2026-05-07
• DOI: 10.1021/acs.organomet.6c00068
• EISSN: 1520-6041
• ISSN: 0276-7333
• Language: English
• Keywords: Yield (engineering); Reagent; Carbene; Ligand (biochemistry); Zinc; Substitution (logic)