The reaction of Power's digalladeltacyclane with Au(PPh 3 )Cl led to formation of a digallium gold complex (2) with both chloride and gold bridging between two gallium atoms. The bonding parameters from the solid-state structure of 2 suggested a 12e − Au center stabilized by weakly coordinated aryl groups. DFT calculations at the M05-2X/[LANL2TZ(f),6-311G(d)] level indicated a Ga−Au−Ga banana bond with no bonding interactions between gallium atoms. The gold carries an NBO charge of −0.0956 e − and is best viewed as an auride. The weak intramolecular interactions between Au p orbitals and σ C−C and σ C−H bonds of the adjacent aromatic rings amount to significant stabilization of the electron-deficient gold center. The digallium complex 2 represents the first structural example of a 12 e − organometallic auride complex, demonstrating its pseudohalide/hydride nature in bonding.
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