Synthesis and Structure of Binuclear Single‐Bridged Bis[(phosphane)gold(I)]halogenonium Complexes

Reactions of (R 3 P)AuX (X = Cl, Br, I) with [(R 3 P)Au] + BF − 4 obtained from (R 3 P)AuCl and AgBF 4 in tetrahydrofuran, lead to cationic binuclear gold(I) complexes of the general formula ([(R 3 P)Au] 2 X} + BF − 4 . A number of chloro‐ (R = Ph, o ‐Tol, Mes, Bzl, Et), bromo‐ (R = Ph, o ‐Tol, Mes) and iodo‐bridged (R = Ph, Mes) complexes of this type have been isolated and identified on the basis of their analytical and spectroscopic data. The crystal structure of bis[(triphenylphosphane)gold(I)]bromonium tetrafluoroborate was determined by single‐crystal X‐ray diffraction. The cations contain two‐coordinate bromine atoms with an Au‐Br‐Au angle of 96.83(3)°.