Evidence for enhanced reactivity in the photofragmentation of the bridged dinuclear system Me2Si[η5-C5H4Fe(CO)2(η1-CH2C6H5)]2 |
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Authors: | Gregory O Nelson Michael E Wright |
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Institution: | Department of Chemistry, University of Arizona, Tucson, Arizona 85721 U.S.A |
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Abstract: | Experimental evidence that the dinuclear complex Me2Siη5-C5H4Fe(CO)2-(η1-CH2C6H5)]2 shows enhanced reactivity over its mononuclear analogy η5-C5H5Fe(CO)2(η1-CH2C6H5 in photogragmentation to produce bibenzyl and FeFe bonded product is presented. Information from a series of competition and crossover experiments indicate that two factors are involved in the enhancement: (1) the ability to photochemically produce a 16-electron unsaturated benzyl unit in close proximity to a saturated partner, and (2) the inability of the FeFe bonded species 4 to quench free benzyl radicals in solution. Chemical reaction of Me2Siη5-C5H4Fe(CO)2(η1-CH2C6H5)]2 with Me3NO produces bibenzyl and establishes that loss of CO is the initial step in the fragmentation reaction. In addition, trapping experiments with 9,10-dihydroanthracene show that bibenzyl is formed from free benzyl radical; BBased on these results an overall mechanism is proposed. |
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