Nucleus-independent chemical shift profiles along the intrinsic distortion path for Jahn-Teller active molecules. Study on the cyclopentadienyl radical and cobaltocene
Abstract
The aromatic/anti-aromatic behavior of the cyclopentadienyl anion (Cp-), bis(eta(5)-cyclopentadienypiron(II) (Fe(Cp)(2)), as well as of the Jahn-Teller (JT) active cyclopentadienyl radical (Cp-center dot) and bis(eta(5)-cyclopentadienyl)cobalt(II) (Co(Cp)(2)) were investigated using density functional theory (DFT) calculations of the nuclear independent chemical shifts (NICS). According to the NICS values, pentagon ring in Fe(Cp)(2) is more aromatic than that of the isolated Cp. The NICS parameters were scanned along the Intrinsic Distortion Path (IDP) for Cp-center dot and Co(Cp)(2) showing anti-aromaticity, which decreased with increasing deviation from the high symmetry D-5h to the low symmetry (LS) C-2v. Changes in the NICS values along the IDP revealed that Co(Cp)(2) in the LS nuclear arrangement has aromatic character, in contrast to the case of Cp-center dot.
Keywords:
vibronic coupling / DFT / aromaticity / metalloceneSource:
Journal of the Serbian Chemical Society, 2015, 80, 7, 877-888Publisher:
- Serbian Chemical Soc, Belgrade
Funding / projects:
- Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (RS-MESTD-Basic Research (BR or ON)-172035)
DOI: 10.2298/JSC141107025A
ISSN: 0352-5139
WoS: 000359326100004
Scopus: 2-s2.0-84938922444
Collections
Institution/Community
IHTMTY - JOUR AU - Anđelković, Ljubica AU - Perić, Marko AU - Zlatar, Matija AU - Gruden-Pavlović, Maja PY - 2015 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1703 AB - The aromatic/anti-aromatic behavior of the cyclopentadienyl anion (Cp-), bis(eta(5)-cyclopentadienypiron(II) (Fe(Cp)(2)), as well as of the Jahn-Teller (JT) active cyclopentadienyl radical (Cp-center dot) and bis(eta(5)-cyclopentadienyl)cobalt(II) (Co(Cp)(2)) were investigated using density functional theory (DFT) calculations of the nuclear independent chemical shifts (NICS). According to the NICS values, pentagon ring in Fe(Cp)(2) is more aromatic than that of the isolated Cp. The NICS parameters were scanned along the Intrinsic Distortion Path (IDP) for Cp-center dot and Co(Cp)(2) showing anti-aromaticity, which decreased with increasing deviation from the high symmetry D-5h to the low symmetry (LS) C-2v. Changes in the NICS values along the IDP revealed that Co(Cp)(2) in the LS nuclear arrangement has aromatic character, in contrast to the case of Cp-center dot. PB - Serbian Chemical Soc, Belgrade T2 - Journal of the Serbian Chemical Society T1 - Nucleus-independent chemical shift profiles along the intrinsic distortion path for Jahn-Teller active molecules. Study on the cyclopentadienyl radical and cobaltocene VL - 80 IS - 7 SP - 877 EP - 888 DO - 10.2298/JSC141107025A ER -
@article{ author = "Anđelković, Ljubica and Perić, Marko and Zlatar, Matija and Gruden-Pavlović, Maja", year = "2015", abstract = "The aromatic/anti-aromatic behavior of the cyclopentadienyl anion (Cp-), bis(eta(5)-cyclopentadienypiron(II) (Fe(Cp)(2)), as well as of the Jahn-Teller (JT) active cyclopentadienyl radical (Cp-center dot) and bis(eta(5)-cyclopentadienyl)cobalt(II) (Co(Cp)(2)) were investigated using density functional theory (DFT) calculations of the nuclear independent chemical shifts (NICS). According to the NICS values, pentagon ring in Fe(Cp)(2) is more aromatic than that of the isolated Cp. The NICS parameters were scanned along the Intrinsic Distortion Path (IDP) for Cp-center dot and Co(Cp)(2) showing anti-aromaticity, which decreased with increasing deviation from the high symmetry D-5h to the low symmetry (LS) C-2v. Changes in the NICS values along the IDP revealed that Co(Cp)(2) in the LS nuclear arrangement has aromatic character, in contrast to the case of Cp-center dot.", publisher = "Serbian Chemical Soc, Belgrade", journal = "Journal of the Serbian Chemical Society", title = "Nucleus-independent chemical shift profiles along the intrinsic distortion path for Jahn-Teller active molecules. Study on the cyclopentadienyl radical and cobaltocene", volume = "80", number = "7", pages = "877-888", doi = "10.2298/JSC141107025A" }
Anđelković, L., Perić, M., Zlatar, M.,& Gruden-Pavlović, M.. (2015). Nucleus-independent chemical shift profiles along the intrinsic distortion path for Jahn-Teller active molecules. Study on the cyclopentadienyl radical and cobaltocene. in Journal of the Serbian Chemical Society Serbian Chemical Soc, Belgrade., 80(7), 877-888. https://doi.org/10.2298/JSC141107025A
Anđelković L, Perić M, Zlatar M, Gruden-Pavlović M. Nucleus-independent chemical shift profiles along the intrinsic distortion path for Jahn-Teller active molecules. Study on the cyclopentadienyl radical and cobaltocene. in Journal of the Serbian Chemical Society. 2015;80(7):877-888. doi:10.2298/JSC141107025A .
Anđelković, Ljubica, Perić, Marko, Zlatar, Matija, Gruden-Pavlović, Maja, "Nucleus-independent chemical shift profiles along the intrinsic distortion path for Jahn-Teller active molecules. Study on the cyclopentadienyl radical and cobaltocene" in Journal of the Serbian Chemical Society, 80, no. 7 (2015):877-888, https://doi.org/10.2298/JSC141107025A . .