Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 20, Issue 20, Pages 13974-13982Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c8cp00424b
Keywords
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Funding
- Japan Society for Promotion of Science (JSPS) under the Joint Research Project of Japan-India Science Cooperative Program
- Department of Science & Technology under the Joint Research Project of Japan-India Science Cooperative Program [DST: DST/INT/JSPS/P-195/2015]
- JSPS [JP23245006, JP26870431]
- Grants-in-Aid for Scientific Research [16H00938, 26870431] Funding Source: KAKEN
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Reactions of the free tantalum cation, Ta+, and tantalum cluster cations, Ta-n(+) (n = 2-10), with ammonia are presented. The reaction of the monomer cation, Ta+, with two molecules of NH3 leads to the formation of TaN2H2+ along with release of two H-2 molecules. The dehydrogenation occurs until the formal oxidation number of the tantalum atom reaches +5. On the other hand, all the tantalum cluster cations, Ta-n(+), react with two molecules of NH3 and form TanN2+ with the release of three H-2 molecules. Further exposure to ammonia showed that TanNmH+ and TanNm+ are produced through successive reactions; a pure nitride and three H-2 molecules are formed for every other NH3 molecule. The nitridation occurred until the formal oxidation number of the tantalum atoms reaches +5 as in the case of TaN2H2+ in contrast to other group 5 elements, i.e., vanadium and niobium, which have been reported to produce nitrides with lower oxidation states. The present results on small gas-phase metal-nitride clusters show correlation with their bulk properties: tantalum is known to form bulk nitrides in the oxidation states of either +5 (Ta3N5) or +3 (TaN), whereas vanadium and niobium form nitrides in the oxidation state of +3 (VN and NbN). Along with DFT calculations, these findings reveal that nitridation is driven by the electron-donating ability of group 5 elements, i.e., electronegativity of the metal plays a key role in determining the composition of the metal nitrides.
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