Syntheses, structures and electrochemical properties of ruthenium(II/III) complexes with tetradentate Schiff base ligands

Ji, Jiao; Chen, Xin; Wang, Chang-Jiu; Jia, Ai‐Quan; Zhang, Qian‐Feng

doi:10.1080/00958972.2019.1566541

Cited by 5 publications

(1 citation statement)

References 28 publications

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“…It was previously reported that cationic 6 was unreactive with H 2 to regenerate 1 in the absence of an appropriate base . Because the nitride signal remained in the IR spectrum, it is likely that the hydride was transferred into the electrophilic imine backbone of the salen ligand to produce an anionic manganese(V) complex. − On the other hand, the reaction of 2 and MnN did not yield the cationic species [(η 5 -C 5 Me 5 )Rh( Me PhI)(MeCN)] + , which was independently prepared and structurally characterized (Supporting Information section S6, Figures S12–S14).…”

Section: Resultsmentioning

confidence: 99%

Catalytic Hydrogenation of a Manganese(V) Nitride to Ammonia

et al. 2020

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The catalytic hydrogenation of a metal nitride to produce free ammonia using a rhodium hydride catalyst that promotes H 2 activation and hydrogen-atom transfer is described. The phenylimine-substituted rhodium complex (η 5 -C 5 Me 5 )Rh-( Me PhI)H ( Me PhI = N-methyl-1-phenylethan-1-imine) exhibited higher thermal stability compared to the previously reported (η 5 -C 5 Me 5 )Rh(ppy)H (ppy = 2-phenylpyridine). DFT calculations established that the two rhodium complexes have comparable Rh− H bond dissociation free energies of 51.8 kcal mol −1 for (η 5 -C 5 Me 5 )Rh( Me PhI)H and 51.1 kcal mol −1 for (η 5 -C 5 Me 5 )Rh(ppy)H. In the presence of 10 mol% of the phenylimine rhodium precatalyst and 4 atm of H 2 in THF, the manganese nitride ( tBu Salen)MnN underwent hydrogenation to liberate free ammonia with up to 6 total turnovers of NH 3 or 18 turnovers of H • transfer. The phenylpyridine analogue proved inactive for ammonia synthesis under identical conditions owing to competing deleterious hydride transfer chemistry. Subsequent studies showed that the use of a non-polar solvent such as benzene suppressed formation of the cationic rhodium product resulting from the hydride transfer and enabled catalytic ammonia synthesis by proton-coupled electron transfer.

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