Molecular Structure of Gaseous Oxopivalate Co(II): Electronic States of Various Multiplicities
Abstract
:1. Introduction
2. Results and Discussions
2.1. Vapor Composition of Cobalt(II) Oxopivalate at T = 410 K
2.2. Electronic States of the Tetranuclear Co(II) Complex with Different Multiplicity. Results of Quantum Chemical Calculations
2.3. Geometric Structure of the Co4O(piv)6 in the Gas Phase. Results of Structural Analysis of Electron Diffraction Data
2.4. Nature of Chemical Bonds in the Co4O(formyl)6 and Co4O(piv)6 Complexes
2.5. Structure of Cobalt Carboxylates in the Gas and Crystalline Phases
3. Materials and Methods
3.1. Conditions of the Synchronous GED/MS Experiments
3.2. Details of Quantum Chemical Calculation of Co4O(formyl)6 in Different Electronic States
3.3. Features of Structural Analysis of GED/MS Data
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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m/e | Ion | Irel, Uioniz = 50 V T = 410 K | Irel [22] Uioniz = 60 V T = 430 K |
---|---|---|---|
1429 | [Co8O2(piv)9O]+ | 2 | |
1344 | [Co8O2(piv)8O2]+ | 5 | |
1093 | [Co6O2(piv)7O2]+ | 1 | |
858 | [Co4O(piv)6]+ | 13 | 10.2 |
757 | [Co4O(piv)5]+ | 100 | 100 |
656 | [Co4O(piv)4]+ | 1 | 11.3 |
571 | [Co4O(piv)3O]+ | 1 | |
555 | [Co4O(piv)3]+ | 1 | 12.1 |
498 | [Co4O(piv)3-tb]+ | 25 | 100.6 |
395 | [Co3O(piv)2]+ | 1 | |
59 | [Co]+ | 5 | 20.7 |
Spin State 1 | |||||||
---|---|---|---|---|---|---|---|
Multiplicity, M | 13 | 11 | 9 | 7 | 5 | 3 | 1 |
CASSCF, ΔE | 1.51 | 1.12 | 0.77 | 0.39 | 0.20 | 0.08 | 0.00 |
XMCQDPT2, ΔE | 6.48 | 4.82 | 3.32 | 1.90 | 0.89 | - | 0.00 |
Qav(MO1) | 1.000 | 1.007 | 1.013 | 1.029 | 1.024 | 1.025 | 1.026 |
Qav(MO2) | 1.000 | 1.007 | 1.013 | 1.020 | 1.020 | 1.024 | 1.026 |
Qav(MO3) | 1.000 | 1.007 | 1.013 | 1.021 | 1.026 | 1.025 | 1.026 |
Qav(MO4) | 1.000 | 1.003 | 1.005 | 1.005 | 1.012 | 1.010 | 1.010 |
Qav(MO5) | 1.000 | 1.000 | 1.000 | 1.000 | 1.000 | 1.000 | 1.000 |
Qav(MO6) | 1.000 | 1.000 | 1.000 | 1.000 | 1.000 | 1.000 | 1.000 |
Qav(MO7) | 1.000 | 1.000 | 1.000 | 1.000 | 1.001 | 1.000 | 1.000 |
Qav(MO8) | 1.000 | 0.999 | 0.999 | 0.998 | 0.995 | 0.998 | 0.998 |
Qav(MO9) | 1.000 | 0.999 | 0.999 | 0.999 | 0.999 | 0.998 | 0.998 |
Qav(MO10) | 1.000 | 0.992 | 0.985 | 0.979 | 0.977 | 0.973 | 0.972 |
Qav(MO11) | 1.000 | 0.992 | 0.985 | 0.970 | 0.975 | 0.973 | 0.972 |
Qav(MO12) | 1.000 | 0.992 | 0.985 | 0.979 | 0.972 | 0.973 | 0.972 |
Complex, Parameter a | Co4O(piv)6 | Co8O2(piv)12 | Co4O(OOCNC9H18)2 | |
---|---|---|---|---|
Method | GED/MS 410 K rh1 (C3) Rf = 4.5% | B3LYP re (C3) | X-ray b [20] | X-ray [28] |
r(OC–Co1) c | 1.975 (5) d p1 e | 1.987 | 1.984 | 1.955 |
r(OC–Co2) | 1.972 (p1) | 1.984 | 1.966 | 1.936, 1.941, 1.954 |
r(Co1–OL) c | 1.963 (5) (p1) | 1.973 | 1.942 | 1.936, 1.939, 1.942 |
r(Co2–OL) | 1.965 (p1) | 1.975 | - | 1.919–1.950 |
r(OL–C) | 1.267/1.265(4) p2 | 1.265/1.263 | 1.247/1.257 | 1.240–1.288 |
r(C-Ct) | 1.537(4) p3 | 1.537 | 1.519 | - |
r(Ct–Cm) | 1.532 (p3) | 1.532 | 1.514 | - |
r(C–H) | 1.079(5) p4 | 1.09 | (0.96) | |
Co1–OC–Co2 | 110.4(6) p5 | 109.5 | 101.4 | 108.3–109.5 |
OL–Co1–OC | 111.8(3) p6 | 110.4 | 113.7 | 110.2–111.9 |
OL–Co1–OL | 107.1(3) (p6) | 108.5 | 104.9 | 107.5 |
Co1–OL–C | 131.8(6) (p5) | 132.5 | 132.7 | 131.9–133.2 |
Co2–OL–C | 128.8(6) (p5) | 130.7 | - | 131.6–132.3 |
OL-C–Ct | 117.2(13) p7 | 117.0 | 119.3 | - |
C–Ct–Cm | 112.1(12) p8 | 111.2 | 112.1 | - |
Cm–Ct–Cm | 108.3(27) p9 | 110.0 | 110.3 | - |
Ct–Cm–H | 111.0(18) p10 | 109.6 | (109.5) | - |
OL–C–Ct–Cm | 5.3(119) p11 | 0.1 | 11.9 | - |
H–Cm–Ct–C | 178.5(45) p12 | 180 | 177.3 | - |
QTAIM Co4O(formyl)6 | NBO Co4O(piv)6 | BCP, QTAIM Co4O(formyl)6 | NBO Co4O(piv)6 | |||||
---|---|---|---|---|---|---|---|---|
Atom | q | qNPA | Bond | ρ | ∇2ρ | ε | δ | P |
Co | 1.41 | 1.20 | Co-Oc | 0.087 | +0.425 | 0.00 | 0.52 | 0.28 |
Oc | −1.32 | −1.20 | Co-OL | 0.087 | +0.456 | 0.01 | 0.47 | 0.30 |
OL | −1.24 | −0.72 | C-OL | 0.383 | −0.592 | 0.07 | 1.06 | 1.37 |
C | 1.74 | 0.84 | ||||||
Natural electron configuration (NBO, Co4O(piv)6) | ||||||||
Oc | [core] 2s(1.75) 2p(5.43) | |||||||
Co | [core] 4s(0.22) 3d(7.25) 4p(0.32) | |||||||
OL | [core] 2s(1.67) 2p(5.04) |
Nozzle-To-Plate Distance, mm | 338 | 598 |
---|---|---|
Electron beam current, µA | 1.4 | 1.0 |
Temperature of effusion cell, K | 410 (5) | 411 (5) |
Accelerating voltage, kV | 83.5 | 81.4 |
Ionization voltage, V | 50 | 50 |
Exposure time, s | 100 | 45 |
Residual gas pressure, Torr | 1.4 × 10−6 | 2.0 × 10−6 |
Scattering angles, Å−1 | 3.0–28.6 | 1.5–16.5 |
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Giricheva, N.I.; Sliznev, V.V.; Alikhanyan, A.S.; Morozova, E.A.; Girichev, G.V. Molecular Structure of Gaseous Oxopivalate Co(II): Electronic States of Various Multiplicities. Int. J. Mol. Sci. 2023, 24, 13224. https://doi.org/10.3390/ijms241713224
Giricheva NI, Sliznev VV, Alikhanyan AS, Morozova EA, Girichev GV. Molecular Structure of Gaseous Oxopivalate Co(II): Electronic States of Various Multiplicities. International Journal of Molecular Sciences. 2023; 24(17):13224. https://doi.org/10.3390/ijms241713224
Chicago/Turabian StyleGiricheva, Nina I., Valery V. Sliznev, Andrey S. Alikhanyan, Ekaterina A. Morozova, and Georgiy V. Girichev. 2023. "Molecular Structure of Gaseous Oxopivalate Co(II): Electronic States of Various Multiplicities" International Journal of Molecular Sciences 24, no. 17: 13224. https://doi.org/10.3390/ijms241713224