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Density Functional Theory and Low-Temperature Matrix Investigations of CO-Loss Photochemistry from [(C5R5)Ru(CO)2]2 (R = H, Me) Complexes

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Abstract

The photochemical CO-loss products of the diruthenium complexes [CpRu(CO) 2]2 (5; Cp = η5-C5H5), [Cp*Ru(CO)2]2 (5*; Cp* = η5-C5(CH3)5) and CpCp*[Ru(CO)2]2 (5′) have been studied experimentally in low-temperature (96 K) matrices in 3-methylpentane by using IR spectroscopy. It is proposed that all three complexes undergo single-CO-loss chemistry but that the products have different structures. The single-CO-loss product from 5 is proposed to have one bridging and two terminal carbonyl ligands, whereas 5* and 5′ generate triply bridged CO-loss products similar to that observed from [CpFe(CO)2]2 and [Cp*Fe(CO)2]2. Double-CO-loss from 5* and 5* 9′ is also apparently observed. Relativistic DFT calculations have been carried out on various isomers of the starting materials and on potential CO-loss products from 5. The calculations suggest that the triply bridged product Cp2Ru2(μ-CO)3 (6) might have a singlet ground state in contrast to the corresponding diiron complex Cp2Fe2(μ-CO)3 (3), which has a triplet ground state.

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Authors and Affiliations

  1. Department of Chemistry, Claflin University, Orangeburg, SC

    Sibrina N. Collins & Bruce E. Bursten

  2. Department of Chemistry, The Ohio State University, Columbus, OH

    Constance M. Brett

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  1. Sibrina N. Collins
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  2. Constance M. Brett
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  3. Bruce E. Bursten
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Collins, S.N., Brett, C.M. & Bursten, B.E. Density Functional Theory and Low-Temperature Matrix Investigations of CO-Loss Photochemistry from [(C5R5)Ru(CO)2]2 (R = H, Me) Complexes. Journal of Cluster Science 15, 469–487 (2004). https://doi.org/10.1007/s10876-004-5770-8

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