Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 138, Issue 40, Pages 13379-13389Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b08009
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- Office of Basic Energy Sciences, Chemical Sciences Division, U.S. Department of Energy [DE-FG-02-05ER15659]
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The hydrogenolysis of titanium nitrogen bonds in a series of bis(cyclopentadienyl) titanium amides, hydrazides and imides by proton coupled electron transfer (PCET) is described. Twelve different N-H bond dissociation free energies (BDFEs) among the various nitrogen-containing ligands were measured or calculated, and effects of metal oxidation state and N-ligand substituent were determined. Two metal hydride complexes, (eta(5)-C5Me5)(py-Ph)Rh-H (py-Ph = 2-pyridylphenyl, [Rh]-H) and (eta-C5R8)(CO)(3)Cr-H ([Cr](R)-H, R= H, Me) were evaluated for formal H atom transfer reactivity and were selected due to their relatively weak M-H bond strengths yet ability to activate and cleave molecular hydrogen. Despite comparable M-H BDFEs, disparate reactivity between the two compounds was observed and was traced to the vastly different acidities of the M H bonds and overall redox potentials of the molecules. With [Rh] H, catalytic syntheses of ammonia, silylamine and N,N-dimethylhydrazine have been accomplished from the corresponding titanium(IV) complex using H-2 as the stoichiometric H atom source. The data presented in this study provides the thermochemical foundation for the synthesis of NH3 by proton coupled electron transfer at a well-defined transition metal center.
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