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Octacoordinate metal carbonyls of lanthanum and cerium: experimental observation and theoretical calculation.

The octacoordinate metal carbonyls La(CO)8(+) and Ce(CO)8(+) were observed in laser vaporization of La and Ce in pure CO gas. The peak intensities in the mass spectra, the infrared photodissociation spectra, and the theoretical calculations indicate that all CO ligands in these two complexes are bonded with the central metal atoms. The CO stretching frequencies in La(CO)8(+) and Ce(CO)8(+) are determined to be 2110 and 2108 cm(-1), respectively. Theoretical studies indicate that the most stable structures for La(CO)8(+) and Ce(CO)8(+) are an Oh geometry at its triplet state and a slightly distorted Oh geometry at its quartet state, respectively. These two complexes represent new octacoordinate metal carbonyls after previously determined U(CO)8(+) and Y(CO)8(+).