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Despite its electron deficiency, boron is versatile in forming multiple bonds. Transition‐metal–boron double bonding is known, but boron–metal triple bonds have been elusive. Two bismuth boron cluster anions, BiB2O− and Bi2B−, containing triple and double B−Bi bonds are presented. The BiB2O− and Bi2B− clusters are produced by laser vaporization of a mixed B/Bi target and characterized by photoelectron...
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