Abstract
Heteronuclear arsenic-iron carbonyl cluster anions AsmFe(CO)n- (m, n = 2, 3) have been generated in the gas phase and investigated by mass-selected infrared photodissociation spectroscopy and density functional theory calculations at the B3LYP/BP86/TPSS levels. All the AsmFe(CO)n- (m, n = 2, 3) cluster anions are determined to contain Fe(CO)n- fragments, which can be regarded as being formed by replacing one arsenic atom of the arsenic clusters Asm+1 with the Fe(CO)n- group. Bonding analyses indicated that each As2Fe(CO)n- (n = 2, 3) cluster anion involves two Fe-As single bonds and one As-As double bond. Each As3Fe(CO)n- (n = 2, 3) cluster anion has three Fe-As single bonds and three As-As single bonds. The Fe(CO)3- group with a 15-electron configuration is valence isoelectronic to the As atom and can serve as a building block for forming heteronuclear arsenic-iron carbonyl clusters.
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