Neutral metal-benzene complexes, Mn(benzene)m (M = Sc to Cu), are produced for all of the 3d transition metals in the gas phase by using the laser vaporization method. These species are characterized by mass spectrometry, photoionization spectroscopy, and chemical probe experiments. Depending on the metal, there are two types of structures for Mn(benzene)m: multiple-decker sandwich structures and metal clusters fully covered with benzene molecules (rice-ball structures). The former sandwich structure is characteristic of the complexes for early transition metals (Sc-V), whereas the latter is formed for late transition metals (Fe-Ni). Electronic structures of M1(benzene)x (x = 1, 2) complexes are investigated through systematic measurements of ionization energies (Ei's).
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