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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| Authors: | Sibrina N. Collins Constance M. Brett Bruce E. Bursten |
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| Affiliation: | (1) Department of Chemistry, Claflin University, Orangeburg, SC;(2) Department of Chemistry, The Ohio State University, Columbus, OH |
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| Abstract: | The photochemical CO-loss products of the diruthenium complexes [CpRu(CO) 2]2 (5; Cp =  5-C5H5), [Cp*Ru(CO)2]2 (5*; Cp* = 5-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( -CO)3 (6) might have a singlet ground state in contrast to the corresponding diiron complex Cp2Fe2(-CO)3 (3), which has a triplet ground state. |
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| Keywords: | Ruthenium photochemistry dimer isomerization DFT |
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