Fluorocarbons have been shown experimentally by Baker and coworkers to combine with the cyclopentadienylcobalt (CpCo) moiety to form fluoroolefin and fluorocarbene complexes as well as fluorinated cobaltacyclic rings. In this connection density functional theory (DFT) studies on the cyclopentadienylcobalt fluorocarbon complexes CpCo(L)(C n F 2n ) (L = CO, PMe 3 ; n = 3 and 4) indicate structures with perfluoroolefin ligands to be the lowest energy structures followed by perfluorometallacycle structures and finally by structures with perfluorocarbene ligands. Thus, for the CpCo(L)(C 3 F 6 ) (L = CO, PMe 3 ) complexes, the perfluoropropene structure has the lowest energy, followed by the perfluorocobaltacyclobutane structure and the perfluoroisopropylidene structure less stable by 8 to 11 kcal mol −1 , and the highest energy perfluoropropylidene structure less stable by more than 12 kcal mol −1 . For the two metal carbene structures Cp(L)CoC(CF 3 ) 2 and Cp(L)CoCF(C 2 F 5 ), the former is more stable than the latter, even though the latter has Fischer carbene character. For the CpCo(L)(C 4 F 8 ) (L = CO, PMe 3 ) complexes, the perfluoroolefin complex structures have the lowest energies, followed by the perfluorometallacycle structures at 10 to 20 kcal mol −1 , and the structures with perfluorocarbene ligands at yet higher energies more than 20 kcal mol −1 above the lowest energy structure. This is consistent with the experimentally observed isomerization of the perfluorinated cobaltacyclobutane complexes CpCo(PPh 2 Me)(–CFR–CF 2 –CF 2 –) (R = F, CF 3 ) to the perfluoroolefin complexes CpCo(PPh 2 Me)(RCFCF 2 ) in the presence of catalytic quantities of HN(SO 2 CF 3 ) 2 . Further refinement of the relative energies by the state-of-the-art DLPNO-CCSD(T) method gives results essentially consistent with the DFT results summarized above.
more »
« less
Domain‐based local pair natural orbital methods within the correlation consistent composite approach
Ab initio composite approaches have been utilized to model and predict main group thermochemistry within 1 kcal mol−1, on average, from well‐established reliable experiments, primarily for molecules with less than 30 atoms. For molecules of increasing size and complexity, such as biomolecular complexes, composite methodologies have been limited in their application. Therefore, the domain‐based local pair natural orbital (DLPNO) methods have been implemented within the correlation consistent composite approach (ccCA) framework, namely DLPNO‐ccCA, to reduce the computational cost (disk space, CPU (central processing unit) time, memory) and predict energetic properties such as enthalpies of formation, noncovalent interactions, and conformation energies for organic biomolecular complexes including one of the largest molecules examined via composite strategies, within 1 kcal mol−1, after calibration with 119 molecules and a set of linear alkanes. © 2019 Wiley Periodicals, Inc.
more » « less- Award ID(s):
- 1900086
- NSF-PAR ID:
- 10458954
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Journal of Computational Chemistry
- Volume:
- 41
- Issue:
- 8
- ISSN:
- 0192-8651
- Page Range / eLocation ID:
- p. 800-813
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Abstract Aluminyl anions are low‐valent, anionic, and carbenoid aluminum species commonly found stabilized with potassium cations from the reaction of Al‐halogen precursors and alkali compounds. These systems are very reactive toward the activation of
σ ‐bonds and in reactions with electrophiles. Various research groups have detected that the potassium atoms play a stabilization role via electrostatic and cationinteractions with nearby (aromatic)‐carbocyclic rings from both the ligand and from the reaction with unsaturated substrates. Since stabilizing K⋯H bonds are witnessed in the activation of this class of molecules, we aim to unveil the role of these metals in the activation of the smaller and less polarizable H2molecule, together with a comprehensive characterization of the reaction mechanism. In this work, the activation of H2utilizing a NON‐xanthene‐Al dimer, [K{Al(NON)}]2( D ) and monomeric, [Al(NON)]−(M ) complexes are studied using density functional theory and high‐level coupled‐cluster theory to reveal the potential role of K+atoms during the activation of this gas. Furthermore, we aim to reveal whetherD is more reactive thanM (or vice versa), or if complicity between the two monomer units exits within theD complex toward the activation of H2. The results suggest that activation energies using the dimeric and monomeric complexes were found to be very close (around 33 kcal mol−1). However, a partition of activation energies unveiled that the nature of the energy barriers for the monomeric and dimeric complexes are inherently different. The former is dominated by a more substantial distortion of the reactants (and increased interaction energies between them). Interestingly, during the oxidative addition, the distortion of the Al complex is minimal, while H2distorts the most, usually over 0.77. Overall, it is found here that electrostatic and induction energies between the complexes and H2are the main stabilizing components up to the respective transition states. The results suggest that the K+atoms act as stabilizers of the dimeric structure, and their cooperative role on the reaction mechanism may be negligible, acting as mere spectators in the activation of H2. Cooperation between the two monomers in D is lacking, and therefore the subsequent activation of H2is wholly disengaged. -
more » « less
Abstract Sulfur dioxide and hypohalous acids (HOX, X=F, Cl, Br, I) are ubiquitous molecules in the atmosphere that are central to important processes like seasonal ozone depletion, acid rain, and cloud nucleation. We present the first theoretical examination of the HOX⋯SO2binary complexes and the associated trends due to halogen substitution. Reliable geometries were optimized at the CCSD(T)/aug‐cc‐pV(T+d)Z level of theory for HOF and HOCl complexes. The HOBr and HOI complexes were optimized at the CCSD(T)/aug‐cc‐pV(D+d)Z level of theory with the exception of the Br and I atoms which were modeled with an aug‐cc‐pwCVDZ‐PP pseudopotential. 27 HOX⋯SO2complexes were characterized and the focal point method was employed to produce CCSDT(Q)/CBS interaction energies. Natural Bond Orbital analysis and Symmetry Adapted Perturbation Theory were used to classify the nature of each principle interaction. The interaction energies of all HOX⋯SO2complexes in this study ranged from 1.35 to 3.81 kcal mol−1. The single‐interaction hydrogen bonded complexes spanned a range of 2.62 to 3.07 kcal mol−1, while the single‐interaction halogen bonded complexes were far more sensitive to halogen substitution ranging from 1.35 to 3.06 kcal mol−1, indicating that the two types of interactions are extremely competitive for heavier halogens. Our results provide insight into the interactions between HOX and SO2which may guide further research of related systems.
-
The catalytic effects of iridium pincer complexes for the hydrogenation of carbon dioxide were investigated with the Unified Reaction Valley Approach (URVA), exploring the reaction mechanism along the reaction path traced out by the reacting species on the potential energy surface. Further details were obtained with the Local Mode Analysis performed at all stationary points, complemented by the Natural Bond Orbital and Bader’s Quantum Atoms in Molecules analyses. Each of the five reaction paths forming the catalytic cycle were calculated at the DFT level complemented with DLPNO-CCSD(T) single point calculations at the stationary points. For comparison, the non-catalytic reaction was also investigated. URVA curvature profiles identified all important chemical events taking place in the non-catalyzed reaction and in the five reactions forming the catalytic cycle, and their contribution to the activation energy was disclosed. The non-catalytic reaction has a large unfavorable activation energy of 76.3 kcal/mol, predominately caused by HH bond cleave in the H2 reactant. As shown by our study, the main function of the iridium pincer catalyst is to split up the one–step non-catalytic reaction into an energy efficient multistep cycle, where HH bond cleavage is replaced by the cleavage of a weaker IrH bond with a small contribution to the activation energy. The dissociation of the final product from the catalyst requires the cleavage of an IrO bond, which is also weak, and contributes only to a minor extent to the activation energy. This, in summary, leads to the substantial lowering of the overall activation barrier by about 50 kcal/mol for the catalyzed reaction. We hope that this study inspires the community to add URVA to their repertoire for the investigation of catalysis reactions.more » « less
-
The correlation consistent Composite Approach for transition metals (ccCA-TM) and density functional theory (DFT) computations have been applied to investigate the fluxional mechanisms of cyclooctatetraene tricarbonyl chromium ((COT)Cr(CO)3) and 1,3,5,7-tetramethylcyclooctatetraene tricarbonyl chromium, molybdenum, and tungsten ((TMCOT)M(CO)3 (M = Cr, Mo, and W)) complexes. The geometries of (COT)Cr(CO)3 were fully characterized with the PBEPBE, PBE0, B3LYP, and B97-1 functionals with various basis set/ECP combinations, while all investigated (TMCOT)M(CO)3 complexes were fully characterized with the PBEPBE, PBE0, and B3LYP methods. The energetics of the fluxional dynamics of (COT)Cr(CO)3 were examined using the correlation consistent Composite Approach for transition metals (ccCA-TM) to provide reliable energy benchmarks for corresponding DFT results. The PBE0/BS1 results are in semiquantitative agreement with the ccCA-TM results. Various transition states were identified for the fluxional processes of (COT)Cr(CO)3. The PBEPBE/BS1 energetics indicate that the 1,2-shift is the lowest energy fluxional process, while the B3LYP/BS1 energetics (where BS1 = H, C, O: 6-31G(d′); M: mod-LANL2DZ(f)-ECP) indicate the 1,3-shift having a lower electronic energy of activation than the 1,2-shift by 2.9 kcal mol−1. Notably, PBE0/BS1 describes the (CO)3 rotation to be the lowest energy process, followed by the 1,3-shift. Six transition states have been identified in the fluxional processes of each of the (TMCOT)M(CO)3 complexes (except for (TMCOT)W(CO)3), two of which are 1,2-shift transition states. The lowest-energy fluxional process of each (TMCOT)M(CO)3 complex (computed with the PBE0 functional) has a ΔG‡ of 12.6, 12.8, and 13.2 kcal mol−1 for Cr, Mo, and W complexes, respectively. Good agreement was observed between the experimental and computed 1H-NMR and 13C-NMR chemical shifts for (TMCOT)Cr(CO)3 and (TMCOT)Mo(CO)3 at three different temperature regimes, with coalescence of chemically equivalent groups at higher temperatures.more » « less
