6533b826fe1ef96bd1284fc3

RESEARCH PRODUCT

Dihydrogen complexes of metalloporphyrins: characterization and catalytic hydrogen oxidation activity

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description

A series of monometallic dihydrogen complexes of the type M(OEP)(L)(H{sub 2}) (M = Ru, Os; L = THF, *Im) was synthesized and characterized by {sup 1}H NMR. The H-H bond length was found to increase when Os was replaced by Ru or when *Im was replaced by THF. The bond distances (as determined by T{sub 1}) range from 0.92 to 1.18 {angstrom}. The first example of a bimetallic bridging dihydrogen complex, Ru{sub 2}(DPB)(*IM){sub 2}(H{sub 2}), was also prepared. The H{sub 2} ligand is simultaneously bound to both Ru-metal centers. High-field {sup 1}H NMR experiments (620 MHz) revealed a -7.37 Hz dipolar splitting of the H{sub 2} ligand for this complex. Analysis of this splitting suggests that the H{sub 2} ligand is bound with the H-H axis perpendicular to the Ru-Ru axis. These complexes were examined as possible catalysts for the oxidation of dihydrogen through prior heterolytic activation of H{sub 2}. Only Ru(OEP)(THF)(H{sub 2}) can be conveniently deprotonated. Ru(OEP)(THF)(H{sub 2}) is also implicated in the Ru-(OEP)((THF){sub 2}) catalyzed isotopic exchange between H{sub 2} and D{sub 2}O in THF solution. Each step for this mechanism has been elucidated. We have also achieved catalytic dihydrogen oxidation using [Ru(OEP)]{sub 2} adsorbed onto graphite. Twomore » mechanisms for this ruthenium porphyrin catalyzed dihydrogen oxidation are presented and compared. 54 refs., 12 figs., 5 tabs.« less