Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Octahedral {Ta6I12} Clusters. / Shamshurin, Maxim V.; Mikhaylov, Maxim A.; Sukhikh, Taisia и др.
в: Inorganic Chemistry, Том 58, № 14, 24.06.2019, стр. 9028-9035.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Octahedral {Ta6I12} Clusters
AU - Shamshurin, Maxim V.
AU - Mikhaylov, Maxim A.
AU - Sukhikh, Taisia
AU - Benassi, Enrico
AU - Tarkova, Alexandra R.
AU - Prokhorikhin, Alexey A.
AU - Kretov, Evgeniy I.
AU - Shestopalov, Michael A.
AU - Abramov, Pavel A.
AU - Sokolov, Maxim N.
N1 - Publisher Copyright: © 2019 American Chemical Society.
PY - 2019/6/24
Y1 - 2019/6/24
N2 - Ta powder reacts with I2 at 650 °C with the formation of Ta6I14, which belongs to the family of {M6(μ-X)12} clusters. It undergoes aquation with the formation of the intensely colored [Ta6I12(H2O)6]2+. The crystal structure was determined for [Ta6I12(H2O)6](BPh4)2·xH2O (Ta-Ta 2.9322(6) Å, Ta-I 2.8104(7) Å, Ta-O 2.3430(5) Å). With DMF, [Ta6I12(DMF)6]I2·xDMF was isolated (Ta-Ta 2.9500(2) Å, Ta-I 2.8310(4) Å, Ta-O 2.2880(7) Å). Cyclic voltammetry of [Ta6I12(H2O)6]2+ shows two consecutive quasi-reversible one-electron oxidations (E1/2 0.61 and 0.92 V vs Ag/AgCl). Reaction of Ta6I14 with Bu4NCN yields (Bu4N)4[Ta6I12(CN)6]·xCH3CN (Ta-Ta 2.9777(4) Å, Ta-I 2.8165(6) Å, Ta-C 2.2730(7) Å). Quantum chemical calculations reproduce well the experimental geometry of the aqua complex and show the essentially Ta-centered nature of both the HOMO and LUMO. The long-term stability of [Ta6I12(H2O)6]2+ solutions can be greatly enhanced in the presence of polystyrenesulfonate (PSS), which forms nanoparticle associates with the aqua complex in water (ca. 1 cluster per 3 PSS monomeric units).
AB - Ta powder reacts with I2 at 650 °C with the formation of Ta6I14, which belongs to the family of {M6(μ-X)12} clusters. It undergoes aquation with the formation of the intensely colored [Ta6I12(H2O)6]2+. The crystal structure was determined for [Ta6I12(H2O)6](BPh4)2·xH2O (Ta-Ta 2.9322(6) Å, Ta-I 2.8104(7) Å, Ta-O 2.3430(5) Å). With DMF, [Ta6I12(DMF)6]I2·xDMF was isolated (Ta-Ta 2.9500(2) Å, Ta-I 2.8310(4) Å, Ta-O 2.2880(7) Å). Cyclic voltammetry of [Ta6I12(H2O)6]2+ shows two consecutive quasi-reversible one-electron oxidations (E1/2 0.61 and 0.92 V vs Ag/AgCl). Reaction of Ta6I14 with Bu4NCN yields (Bu4N)4[Ta6I12(CN)6]·xCH3CN (Ta-Ta 2.9777(4) Å, Ta-I 2.8165(6) Å, Ta-C 2.2730(7) Å). Quantum chemical calculations reproduce well the experimental geometry of the aqua complex and show the essentially Ta-centered nature of both the HOMO and LUMO. The long-term stability of [Ta6I12(H2O)6]2+ solutions can be greatly enhanced in the presence of polystyrenesulfonate (PSS), which forms nanoparticle associates with the aqua complex in water (ca. 1 cluster per 3 PSS monomeric units).
KW - MAGNETIC-PROPERTIES
KW - BASIS-SETS
KW - HEXANUCLEAR
KW - NIOBIUM
KW - TANTALUM
KW - HALIDE
KW - COMPLEXES
KW - THERMOCHEMISTRY
KW - SPECTRA
KW - VALENCE
UR - http://www.scopus.com/inward/record.url?scp=85069889350&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.9b00364
DO - 10.1021/acs.inorgchem.9b00364
M3 - Article
C2 - 31247827
AN - SCOPUS:85069889350
VL - 58
SP - 9028
EP - 9035
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 14
ER -
ID: 21043646