Absorption spectroscopy of (Ind)Ni(PPh3)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)2 (M = Ni, Ru; Ind = indenyl)

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Abstract
The electronic structures of two types of transition metal indenyl complexes have been studied. The first type, a series of (Ind)Ni(PPh3)X compounds (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) was investigated by absorption spectroscopy and Extended Hückel Molecular Orbital calculations. The energy differences between calculated levels are in good agreement with experimental band positions. For example, the lowest energy singlet–singlet band maximum for (Ind)Ni(PPh3)Cl is at 19 500 cm−1 and the calculated HOMO–LUMO difference is 19 817 cm−1. For X = Me, the calculated energy difference increases to 21 930 cm−1 and the corresponding absorption band is at 22 500 cm−1. The influence of the metal–ligand interactions on the molecular orbitals is discussed. The second category of indenyls, the bis(indenyl) compounds of Ni and Ru, show absorption spectra that are markedly different from those of nickelocene and ruthenocene. For example, in comparison to nickelocene, the first absorption band of Ni(Ind)2 is 5700 cm−1 higher in energy and is more intense by two orders of magnitude; in contrast, the first absorption maximum of Ru(Ind)2 is 6600 cm−1 lower in energy than observed for ruthenocene. The characteristics and relaxation dynamics of the lowest energy excited states are discussed. Key words: absorption spectroscopy, indenyl, nickel, ruthenium, EHMO analysis.