Quantitative Assessment of Tetrel Bonding Utilizing Vibrational Spectroscopy
Abstract
:1. Introduction
2. Computational Methods
3. Results and Discussion
3.1. Tetrel Bonds (TB) in Neutral Complexes
3.2. Charge-Assisted Tetrel Bonds
3.3. Tetrel Bonds vs. Other Noncovalent Interactions
4. Conclusions
- Tetrel bonding becomes stronger as the atomic mass of the tetrel center increases as a consequence of increasing the polarizability.
- For X−TH3···NH3 complexes, the tetrel bond strength weakens in the order (X = F) > (X = Cl) > (X = Br) ≥ (X = OH) as the magnitude of the -hole decreases in the order of F−TH3>Cl−TH3>Br−TH3≥ OH−TH3.
- Successive fluorination of SiH4 impacts both the strength and the nature of the tetrel bond. The successive fluorinations result in stronger tetrel bonding as a consequence of (i) higher at the -hole region; (ii) the partial covalent character of the interaction; (iii) higher electron delocalization that occurs from the highest occupied molecular orbital (HOMO) of the T acceptor to the lowest unoccupied molecular orbital (LUMO) of the T donor. In this series, the binding energy trend deviates from BSO n values due to the high energetic cost associated with the geometric deformation of the monomers upon complexation () which is a consequence of the exchange-repulsion between the lone pair orbitals of the peripheral atoms of the T donor.
- Tetrel bonds in double bonded C donors, e.g., CO2 with NH3, are weak and electrostatic in nature. Substituting a C=O double bond with an electron withdrawing group (F atoms) strengthens the tetrel bond.
- A positively-charged Tdonor or negatively-charged T-acceptor strengthens the tetrel bond. It creates higher at the -hole, resulting in a stronger electrostatic interaction.
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
Abbreviations
ACS | Adibatic connection scheme |
BSO n | Bond strength order |
CCSD(T) | Coupled cluster theory with singles, doubles, and perturbative triples |
CT | Intermonomer charge transfer |
EDG | Electron donating group |
EWG | Electron withdrawing group |
HOMO | Highest occupied molecular orbital |
LUMO | Lowest unoccupied molecular orbital |
NBO | Natural bond orbital |
NCI | Noncovalent interaction |
NPA | Natural population analysis |
TB | Tetrel bond |
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# | Complex (symm.) | E | r | r | CT | n | n | ||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
TA | XT | TA | TA | TA | TA | XT | XT | ||||||
Neutral tetrel bonds involving C donors | |||||||||||||
1 | FCH3···FH (C3v) | −1.50 | −1.29 | 0.01 | 2.972 | 1.392 | 2 | 0.034 | 0.012 | 0.045 | 0.073 | 5.018 | 1.038 |
2 | FCH3···OH2 (Cs) | −2.10 | −1.87 | 0.02 | 3.035 | 1.394 | 3 | 0.041 | 0.012 | 0.055 | 0.081 | 4.956 | 1.030 |
3 | FCH3···NH3 (C3v) | −2.25 | −2.05 | 0.02 | 3.218 | 1.395 | 5 | 0.040 | 0.009 | 0.049 | 0.076 | 4.912 | 1.025 |
4 | ClCH3···NH3 (C3v) | −2.08 | −1.88 | 0.02 | 3.289 | 1.798 | 6 | 0.037 | 0.008 | 0.043 | 0.071 | 2.943 | 0.768 |
5 | BrCH3···NH3 (C3v) | −2.00 | −1.80 | 0.02 | 3.304 | 1.953 | 6 | 0.037 | 0.008 | 0.041 | 0.069 | 2.515 | 0.703 |
6 | (HO)CH3···NH3 (Cs) | −1.38 | −1.21 | 0.01 | 3.362 | 1.429 | 3 | 0.031 | 0.008 | 0.032 | 0.060 | 4.652 | 0.994 |
7 | CF4···NH3 (C3v) | −1.62 | −1.24 | 0.06 | 3.426 | 1.328 | 1 | 0.030 | 0.007 | 0.044 | 0.072 | 5.926 | 1.140 |
Neutral tetrel bonds involving Si donors | |||||||||||||
8 | FSiH3···FH (Cs) | −2.28 | −1.85 | 0.06 | 2.964 | 1.617 | 9 | 0.055 | 0.005 | 0.062 | 0.087 | 4.970 | 1.032 |
9 | FSiH3···OH2 (Cs) | −4.20 | −3.61 | 0.35 | 2.774 | 1.623 | 25 | 0.092 | 0.002 | 0.088 | 0.106 | 4.762 | 1.007 |
10 | FSiH3···NH3 (C3v) | −6.80 | −5.94 | 2.11 | 2.523 | 1.637 | 81 | 0.179 | −0.033 | 0.103 | 0.116 | 4.209 | 0.940 |
11 | ClSiH3···NH3 (C3v) | −6.13 | −5.41 | 2.02 | 2.580 | 2.117 | 84 | 0.165 | −0.024 | 0.073 | 0.095 | 1.941 | 0.607 |
12 | BrSiH3···NH3 (C3v) | −6.11 | −5.35 | 2.23 | 2.566 | 2.290 | 90 | 0.170 | −0.027 | 0.066 | 0.090 | 1.505 | 0.526 |
13 | (HO)SiH3···NH3 (Cs) | −4.13 | −3.61 | 0.68 | 2.825 | 1.680 | 42 | 0.108 | −0.003 | 0.070 | 0.093 | 4.065 | 0.921 |
14 | SiH4···NH3 (C3v) | −2.27 | −1.97 | 0.15 | 3.202 | 1.490 | 18 | 0.060 | 0.004 | 0.049 | 0.076 | 2.793 | 0.746 |
15 | SiF2H2···NH3 (Cs) | −6.99 | −5.73 | 4.74 | 2.400 | 1.613 | 95 | 0.225 | −0.066 | 0.083 | 0.103 | 4.573 | 0.985 |
16a | SiF3H···NH3 (Cs) | −7.66 | −5.77 | 11.77 | 2.205 | 1.617 | 139 | 0.320 | −0.126 | 0.249 | 0.191 | 4.698 | 1.000 |
16b | HSiF3···NH3 (C3v) | −6.30 | −4.14 | 21.22 | 2.104 | 1.474 | 172 | 0.390 | −0.149 | 0.493 | 0.280 | 2.974 | 0.772 |
17 | SiF4···NH3 (C3v) | −11.40 | −8.86 | 21.15 | 2.072 | 1.609 | 176 | 0.419 | −0.164 | 0.678 | 0.335 | 5.046 | 1.041 |
Neutral tetrel bonds involving Ge donors | |||||||||||||
18 | FGeH3···NH3 (C3v) | −7.77 | −7.18 | 1.40 | 2.624 | 1.816 | 44 | 0.169 | −0.008 | 0.149 | 0.143 | 4.125 | 0.929 |
19 | ClGeH3···NH3 (C3v) | −6.22 | −5.75 | 1.07 | 2.755 | 2.216 | 64 | 0.134 | −0.001 | 0.103 | 0.116 | 1.921 | 0.604 |
20 | BrGeH3···NH3 (C3v) | −6.01 | −5.53 | 1.07 | 2.776 | 2.375 | 66 | 0.132 | 0.000 | 0.097 | 0.112 | 1.591 | 0.543 |
21 | (HO)GeH3···NH3 (Cs) | −4.58 | −4.18 | 0.50 | 2.910 | 1.818 | 39 | 0.101 | 0.004 | 0.089 | 0.107 | 3.49 | 0.845 |
22 | GeH4···NH3 (C3v) | −1.99 | −1.79 | 0.09 | 3.323 | 1.550 | 15 | 0.052 | 0.005 | 0.047 | 0.074 | 2.580 | 0.713 |
Neutral tetrel bonds involving double bonded C or Si donors | |||||||||||||
23 | CO2···NH3 (Cs) | −3.09 | −2.84 | 0.11 | 2.922 | 1.167 | 5 | 0.107 | 0.002 | 0.079 | 0.100 | 15.183 | 1.938 |
24 | SCO···NH3 (Cs) | −1.97 | −1.69 | 0.02 | 3.209 | 1.573 | 3 | 0.046 | 0.009 | 0.047 | 0.074 | 7.081 | 1.260 |
25 | CF2O···NH3 (Cs) | −5.55 | −4.82 | 0.27 | 2.687 | 1.178 | 12 | 0.113 | 0.005 | 0.122 | 0.127 | 14.393 | 1.880 |
26a | CF2S···NH3 (Cs) | −3.91 | −3.23 | 0.11 | 2.897 | 1.607 | 9 | 0.078 | 0.008 | 0.086 | 0.105 | 6.397 | 1.190 |
26b | CF2S···NH3 (Cs) | 1.45 | 4.28 | 24.13 | 1.587 | 1.701 | 545 | 1.388 | −1.339 | 1.414 | 0.508 | 3.828 | 0.891 |
27 | SiF2O···NH3 (Cs) | −44.14 | −42.16 | 7.96 | 1.917 | 1.529 | 229 | 0.569 | −0.224 | 1.838 | 0.589 | 8.803 | 1.425 |
Charge-assisted interactions | |||||||||||||
28 | CH3+···NH3 (C3v) | −110.25 | −109.01 | 24.95 | 1.511 | 1.087 | 329 | 1.517 | −1.952 | 3.766 | 0.882 | 5.458 | 1.088 |
29 | FNH3+···NH3 (C3v) | −23.14 | −22.77 | 0.43 | 2.619 | 1.374 | 35 | 0.142 | 0.012 | 0.364 | 0.236 | 5.226 | 1.062 |
30 | FCH3···Cl− (C3v) | −9.77 | −9.34 | 0.39 | 3.179 | 1.419 | 23 | 0.064 | 0.010 | 0.128 | 0.131 | 4.155 | 0.933 |
31 | FSiH3···Cl− (C3v) | −20.73 | −19.49 | 12.03 | 2.504 | 1.703 | 263 | 0.277 | −0.115 | 0.370 | 0.238 | 2.793 | 0.746 |
32 | FGeH3···Cl− (C3v) | −26.10 | −25.09 | 10.71 | 2.566 | 1.892 | 238 | 0.290 | −0.069 | 0.455 | 0.268 | 2.451 | 0.693 |
33 | CO2···Cl− (Cs) | −7.45 | −6.99 | 1.44 | 2.920 | 1.170 | 31 | 0.107 | 0.002 | 0.109 | 0.120 | 14.879 | 1.916 |
34 | SCO···Cl− (Cs) | −5.36 | −4.96 | 0.52 | 3.143 | 1.581 | 24 | 0.073 | 0.006 | 0.079 | 0.100 | 6.568 | 1.208 |
35 | CF2S···Cl− (Cs) | −16.81 | −13.83 | 32.63 | 1.898 | 1.725 | 798 | 1.031 | −0.593 | 1.100 | 0.441 | 3.414 | 0.835 |
# | Monomers | (X) | r(XT) | (XT) | n(XT) | Dipole | |
---|---|---|---|---|---|---|---|
36 | F−CH3 | 0.90 | 1.389 | 5.107 | 1.048 | 1.88 | 2.5 |
37 | Cl−CH3 | 0.76 | 1.792 | 3.068 | 0.786 | 1.92 | 4.3 |
38 | Br−CH3 | 0.69 | 1.948 | 2.616 | 0.718 | 1.86 | 5.4 |
39 | HO−CH3 | 0.47 | 1.426 | 4.749 | 1.006 | 3.1 | |
40 | F−CF3 | 0.93 | 1.321 | 6.204 | 1.170 | 0.00 | 2.8 |
41 | F−SiH3 | 1.64 | 1.613 | 5.120 | 1.049 | 1.38 | 4.1 |
42 | Cl−SiH3 | 1.51 | 2.072 | 2.799 | 0.746 | 1.41 | 6.2 |
43 | Br−SiH3 | 1.46 | 2.238 | 2.321 | 0.672 | 1.38 | 7.4 |
44 | HO−SiH3 | 1.14 | 1.664 | 4.517 | 0.978 | 4.9 | |
45 | H−SiH3 | 0.81 | 1.483 | 2.903 | 0.762 | 0.00 | 4.6 |
46 | F−SiH2F | 1.72 | 1.597 | 5.497 | 1.092 | 3.5 | |
47a | F−SiF2H | 1.78 | 1.583 | 5.884 | 1.135 | 3.8 | |
47b | H−SiF3 | 1.44 | 1.458 | 3.273 | 0.815 | 1.43 | 3.8 |
48 | F−SiF3 | 1.98 | 1.571 | 6.281 | 1.178 | 0.00 | 3.3 |
49 | F−GeH3 | 1.93 | 1.793 | 4.951 | 1.030 | 2.25 | 4.7 |
50 | Cl−GeH3 | 1.66 | 2.175 | 2.491 | 0.699 | 2.04 | 6.9 |
51 | Br−GeH3 | 1.57 | 2.330 | 2.091 | 0.633 | 1.93 | 8.1 |
52 | HO−GeH3 | 1.33 | 1.802 | 3.872 | 0.896 | 5.5 | |
53 | H−GeH3 | 0.73 | 1.542 | 2.693 | 0.730 | 0.00 | 5.2 |
54 | O=CO | 1.18 | 1.167 | 15.613 | 1.969 | 0.00 | 2.6 |
55 | S=CO | 0.64 | 1.575 | 7.227 | 1.275 | 0.68 | 5.2 |
56 | O=CF2 | 1.85 | 1.177 | 14.680 | 1.902 | 1.00 | 2.8 |
57 | S=CF2 | 1.29 | 1.603 | 6.626 | 1.214 | 0.16 | 5.2 |
58 | O=SiF2 | 3.46 | 1.517 | 9.243 | 1.465 | 2.31 | 4.0 |
59 | CH3+ | 10.01 | 0.00 | 1.3 | |||
60 | F−NH3+ | 8.58 | 1.368 | 5.642 | 1.109 | 4.78 | 1.7 |
# | Complex | (X-Si) | (Si-R) | (Si-R’) | (Si-R”) |
---|---|---|---|---|---|
10 | FSiH3···NH3 | 15.7 | 2.4 | 2.4 | 2.4 |
15 | SiF2H2···NH3 | 12.7 | 6.2 | 3.1 | 3.1 |
16a | SiF3H···NH3 | 16.3 | 11.9 | 11.9 | 7.5 |
16b | SiF3H···NH3 | 11.4 | 23.5 | 23.5 | 23.5 |
16b | SiHF3···NH3 | 7.9 | 16.8 | 16.8 | 16.8 |
17 | SiF4···NH3 | 20.7 | 19.5 | 19.5 | 19.5 |
Complex | r | CT | n | n | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|
TA | TA | TA | TA | TA | XT | XT | |||||
F2···OH2 (Cs) | −1.42 | −1.15 | 2.662 | 0.005 | 0.066 | 0.022 | 0.057 | 0.083 | 4.488 | 0.974 | |
Cl2···OH2 (Cs) | −2.98 | −2.62 | 2.808 | 0.015 | 0.098 | 0.018 | 0.097 | 0.112 | 2.896 | 0.761 | |
FCl···OH2 (Cs) | −5.22 | −4.75 | 2.566 | 0.032 | 0.163 | 0.016 | 0.170 | 0.154 | 3.967 | 0.909 | |
FSH···OH2 (Cs) | −5.69 | −5.15 | 2.659 | 0.028 | 0.138 | 0.010 | 0.152 | 0.144 | 4.011 | 0.914 | |
FPH2···OH2 (Cs) | −4.63 | −4.02 | 2.780 | 0.021 | 0.107 | 0.006 | 0.118 | 0.125 | 4.198 | 0.938 | |
F2···NH3 (C3v) | −2.00 | −1.69 | 2.615 | 0.017 | 0.097 | 0.027 | 0.062 | 0.087 | 3.821 | 0.890 | |
Cl2···NH3 (C3v) | −4.92 | −4.43 | 2.664 | 0.055 | 0.172 | 0.006 | 0.132 | 0.133 | 2.370 | 0.680 | |
FCl···NH3 (C3v) | −10.13 | −9.39 | 2.320 | 0.145 | 0.358 | −0.058 | 0.311 | 0.216 | 2.687 | 0.729 | |
FSH···NH3 (Cs) | −8.23 | −7.58 | 2.512 | 0.081 | 0.235 | −0.020 | 0.194 | 0.166 | 3.309 | 0.820 | |
FPH2···NH3 (Cs) | −6.81 | −6.10 | 2.663 | 0.057 | 0.171 | −0.012 | 0.144 | 0.140 | 3.794 | 0.886 | |
FCl···Cl− (C∞v) | −30.07 | −28.98 | 2.316 | 0.496 | 0.547 | −0.161 | 0.855 | 0.382 | 1.212 | 0.465 | |
FSH···Cl− (Cs) | −23.46 | −22.48 | 2.493 | 0.305 | 0.377 | −0.092 | 0.443 | 0.264 | 1.466 | 0.518 | |
FPH2···Cl− (Cs) | −19.62 | −18.62 | 2.649 | 0.208 | 0.266 | −0.058 | 0.307 | 0.214 | 2.136 | 0.641 |
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Sethio, D.; Oliveira, V.; Kraka, E. Quantitative Assessment of Tetrel Bonding Utilizing Vibrational Spectroscopy. Molecules 2018, 23, 2763. https://doi.org/10.3390/molecules23112763
Sethio D, Oliveira V, Kraka E. Quantitative Assessment of Tetrel Bonding Utilizing Vibrational Spectroscopy. Molecules. 2018; 23(11):2763. https://doi.org/10.3390/molecules23112763
Chicago/Turabian StyleSethio, Daniel, Vytor Oliveira, and Elfi Kraka. 2018. "Quantitative Assessment of Tetrel Bonding Utilizing Vibrational Spectroscopy" Molecules 23, no. 11: 2763. https://doi.org/10.3390/molecules23112763