Electron Delocalization and Relativistic Effects in the Electronic Structure and NMR Parameters of [Cp*3M3Se2]2+ (M = Rh, Ir) Complex Cations Full article
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Journal of Structural Chemistry
ISSN: 1573-8779 , E-ISSN: 0022-4766 |
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| Output data | Year: 2023, Volume: 64, Number: 8, Pages: 1391-1398 Pages count : 8 DOI: 10.1134/s0022476623080048 | ||
| Tags | 77Se NMR, DFT, NBO, AIM, metal–metal bonds | ||
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Abstract:
The question about the presence or absence of metal–metal bonds in [Cp*3M3Se2]2+ complex cations, where M = Rh, Ir, is considered by density functional theory (DFT) methods. The bonding is analyzed by AIM, Foster–Boys localized orbitals, and NBO methods. It is shown that in these systems, due to the strong electron delocalization, it is better to speak about three-center M–M–Se and four-center M–Se–M–Se bonds rather than two-center metal–metal bonds. The compositions of bond orbitals differ in rhodium and iridium complexes. The analysis of contributions of different NBOs to the magnetic shielding of Se reveals that the difference in 77Se NMR chemical shifts is related to a change in the contribution of the Se lone pair, antibonding M–Se orbitals, and an admixture of orbitals of the second Se atom in the iridium complex rather than the presence or absence of metal–metal bonds.
Cite:
Mirzaeva I.V.
Electron Delocalization and Relativistic Effects in the Electronic Structure and NMR Parameters of [Cp*3M3Se2]2+ (M = Rh, Ir) Complex Cations
Journal of Structural Chemistry. 2023. V.64. N8. P.1391-1398. DOI: 10.1134/s0022476623080048 WOS Scopus OpenAlex
Electron Delocalization and Relativistic Effects in the Electronic Structure and NMR Parameters of [Cp*3M3Se2]2+ (M = Rh, Ir) Complex Cations
Journal of Structural Chemistry. 2023. V.64. N8. P.1391-1398. DOI: 10.1134/s0022476623080048 WOS Scopus OpenAlex
Original:
Мирзаева И.В.
Делокализация электронов и релятивистские эффекты в электронном строении и параметрах ЯМР комплексных катионов Cp*3M3Se2]2+ (M = Rh, Ir)
Журнал структурной химии. 2023. Т.64. №8. 113998 :1-8. DOI: 10.26902/jsc_id113998 РИНЦ OpenAlex
Делокализация электронов и релятивистские эффекты в электронном строении и параметрах ЯМР комплексных катионов Cp*3M3Se2]2+ (M = Rh, Ir)
Журнал структурной химии. 2023. Т.64. №8. 113998 :1-8. DOI: 10.26902/jsc_id113998 РИНЦ OpenAlex
Dates:
| Submitted: | May 9, 2023 |
| Accepted: | May 24, 2023 |
| Published print: | Aug 31, 2023 |
| Published online: | Aug 31, 2023 |
Identifiers:
| Web of science: | WOS:001059706000004 |
| Scopus: | 2-s2.0-85170267240 |
| OpenAlex: | W4386334031 |