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Ligand-Dependent Multi-State Reactivity in Cobalt(III)-Catalyzed C-H Activations Pengchen Ma, and Hui Chen ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.8b04532 • Publication Date (Web): 17 Jan 2019 Downloaded from http://pubs.acs.org on January 17, 2019
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Ligand-Dependent Multi-State Reactivity in Cobalt(III)Catalyzed C-H Activations Pengchen Ma†,‡ and Hui Chen*,† † Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China ‡ University of Chinese Academy of Sciences, Beijing 100049, P. R. China
ABSTRACT: Cobalt(III)-promoted C-H activation reactions have witnessed explosive progress in recent few years. However, the roles played by the various spin states of Co(III) center in C-H activation reactivity remain elusive. To resolve this conundrum, herein we go beyond the commonly used DFT methods to explore three typical Co(III)-promoted C-H activation systems. Our high level coupled cluster modelings demonstrate that multi-state reactivity (MSR) involving three spin states operates for C(sp2)-H and C(sp3)-H activations with non-Cp-Co(III) type catalyst, while single-state reactivity (SSR) involving only one singlet spin state operates for C(sp2)-H activation with Cp-Co(III) type catalyst. This ligand-dependent reaction scenario of MSR/SSR reveals the high complexity in mechanisms of Co(III)-promoted C-H activations. KEYWORDS: C-H activation, cobalt-catalyzed, multi-state reactivity, two-state reactivity, spin states, ligand effect
1. INTRODUCTION In the active research field of C-H activation/functionalization that transforms inert C-H bonds directly into various functional groups, the platinum group metals (Ru, Rh, Pd, Ir, Pt) are dominant players.1 However, the scarcity of these 4d and 5d noble and precious metals makes their usage not sustainable. As a result, exploring the potentials of their 3d congeners (Fe, Co, Ni) in C-H activation/functionalization reactions, which are more earthabundant and much less costly, has recently attracted immense research interests.2 Among these base metals, on the basis of group similarity in periodic table, catalysts containing Co(III) are particularly appealing due to the exceptional catalytic abilities of Rh(III) and Ir(III) in C-H activations.1h,i Indeed, in the past few years, catalytic systems containing Co(III) have witnessed explosive progress in C-H activation/functionalization reactions.3-28 Currently, there are mainly two types of Co(III) catalysts for CH activation/functionalization reactions in literature. As shown in Scheme 1, one type, first reported by Kanai, Matsunaga and their coworkers in 2013,3a is characterized by bearing a cyclopentadienyl (Cp) type ligand; the other type, introduced by Daugulis et al. in 2014,4a has no Cp type ligand, but the existence of bidentate directing groups29 in the substrates is indispensible in most cases (Mn2+ or Ag+ is oxidant to oxidize Co(II) precatalyst to Co(III) in the presence of bidentate directing groups). Most C-H activations
Scheme 1. Selected Typical C-H Activation Reactions Promoted by Co(III), Including (a) C(sp2)-H and (b) C(sp3)-H Activation by Non-Cp-Co(III) Catalysts, (c) C(sp2)-H Activation by Cp-Co(III) Catalyst (a) O N
HN
Co(OAc)2 4H2O(10 mol%) Diphenylacetylene NaOPiv(2 equiv) Mn(OAc)2(1 equiv)
O N
N
CF3CH2OH,80°C,6h
H
Daugulis et al. ref 4a
Ph Ph
(b) O N
HN
Co(OAc)2(10 mol%),Ag2CO3(2.5 eq) N
PhCO2Na(0.5 eq),PhCl,150°C,24h
N
O
Ge et al. ref 5
H
(c) N
N H +
OH
[Cp*Co(CO)I2] (10 mol %) AgOTf (20 mol %) AgOAc (20 mol %) DCE 60°C,8h
N
N
Kanai et al. ref 3d
promoted by Co(III) are of C(sp2)-H type, with only a few exceptions of C(sp3)-H type reported by Ge,5 Zhang,6a Gaunt,7a Lei,7b Sundararaju,8a,b,e and Shi27c,d groups. In particular, recent mechanistic experimental results of the cobaltacycles have verified the involvement of C-H activation step in the Cp-Co(III)-catalyzed CH functionalization.19,22e These and other experimental results for cobaltacycles also indicate that mononuclear Co(III) species are able to promote C-H activation process.12a,19,22e However, the possibility of involvement of polynuclear cobalt species in C-H activation cannot be ruled out currently, especially considering that acetate could act as bridging ligand. Along with the extensive experimental studies for exploring the C-H activations by Co(III), there are already many computational investigations for CpCo(III) and non-Cp-Co(III) type systems.3c-d,m,6g,8b-d,i,9d,i,10g,11ce,q,r,12a,b,18y,26g,27e Most of these computational studies were focused on reaction mechanism of only one type of system. Importantly, as a fundamental issue for understanding the general reactivity of Co(III)-promoted C-H activation, roles of various spin states of Co(III) concerning their accessibility and reactivity, remain unclear. Without knowing more about this issue, gaining the general understanding for homogeneous C-H activation reactivity promoted by Co(III) is still an unmet challenge. The involvement and mediation of multiple spin states in base metal catalysis have recently attracted a lot of research inter-
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ests.30,31 Of particular relevance to the Co(III)-promoted C-H activation, through high level quantum chemical modeling based on coupled cluster approach, we recently found that both Fe(III) and Fe(II) in catalytic organometallic systems can promote C-H activation via two-state reactivity (TSR) scenario. In this TSR scenario, the low-spin state cuts through the high spin state reaction profile and exhibits higher reactivity.32 Considering that iron is adjacent to cobalt in periodic table, and Co(III) and Fe(II) have the same d6 valence shell, it is intriguing to know whether C-H activations promoted by Co(III) also involve more than one spin state. In all previous theoretical modelings of Co(III)-promoted CH activations, DFT methods were unexceptionally employed.3cd,m,6g,8b-d,i,9d,i,10g,11c-e,q,r,12a,b,18y,26g,27e Unfortunately, predicting accurate spin state energetics for first-row transition metals is still a very challenging task for commonly used DFT methods.33 To tackle the multiple spin state issue for Co(III)-promoted C-H activations, high-level ab initio electronic structure methods are in order. However, to our best knowledge, there is still no example to go beyond the DFT methods for modeling the Co(III)-promoted C-H activation. In this work, based on extensive combined highlevel coupled cluster and DFT calculations,34 we discovered that Co(III)-promoted C-H activations can have complicated multistate reactivity31a,b (MSR) that are dependent on the ligand type of Co(III) catalyst. In this mechanistic framework, a unified mechanistic understanding for C-H activation reactivity by Cp and nonCp types of Co(III) systems is achieved. 2. COMPUTATIONAL DETAILS All molecular geometries were optimized in gas phase, employing UB3LYP35 functional combined with def2-SVP basis set36 for all atoms. Optimized minima and transition states (TSs) were verified by harmonic vibrational analysis to have no and one proper imaginary frequency, respectively. The thermal correction for Gibbs energy (ΔGthermal) was calculated in these harmonic vibrational analysis at the corresponding experimental temperatures. To refine the calculated energy, single point calculations with larger basis set were then done based on these optimized structures, by using UB3LYP functional with def2-TZVP basis set,36 including Grimme’s DFT empirical dispersion correction (DFT-D3) with the original short range damping.37 Solvent effect was also modeled in these single point calculations by employing SMD continuum solvation model,38 taking experimental solvents in each calculations. Gibbs free energy correction (ΔGsolv) was obtained from the energy difference between gas phase and solution calculations. The H/D semiclassical kinetic isotope effect (KIE) of the C−H activation was calculated using eq. 1 derived from the Eyring model, in which the free energies of activation (ΔG‡) were calculated at the reaction temperature. All DFT geometry optimizations and single point calculations were performed with Gaussian 09 program.39 KIE = KH/KD = exp[(ΔG‡D - ΔG‡H)/RT]
(1)
To render more accurate electronic energies over the DFT data, domain based local pair-natural orbital coupled cluster (abbreviated as DLPNO-CCSD(T)) method40 were performed with ORCA.41 To avoid convergence problem in systems containing first-row transition metals, instead of Hartree-Fock (HF) reference, we employed DFT(UB3LYP) Kohn-Sham orbital reference in DLPNO-CCSD(T) calculations. For all atoms, cc-pVDZ (abbreviated as VDZ) and cc-pVTZ (abbreviated as VTZ) basis sets42 were employed in DLPNO-CCSD(T) calculations, and two-point complete basis set (CBS) limit extrapolation from VDZ and VTZ data was carried out by using the inverse quartic equation Etotal,n = Etotal,CBS + A/(n+1/2)4 (cardinal number n = 2, 3) for total electronic energy to alleviate the basis set incompleteness error.43 The
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final reported Gibbs free energies used for reaction energy profiles in Figures 1, 2, and 3 were calculated using eq. 2, in which EDLCC is Etotal,CBS. Gfinal = EDLCC + ΔGthermal + ΔGsolv
(2)
The Co 3s3p core-valence correlation and scalar relativistic effects were tested for the C(sp3)-H activations with the non-CpCo(III) type ligand (system b), cc-pwCVDZ-DK/cc-pVDZ-DK (abbreviated as wDZ) and cc-pwCVTZ-DK/cc-pVTZ-DK (abbreviated as wTZ) basis sets42 were employed for Co/rest atoms in the test calculations, the scalar relativistic effect was taken into account by using the second-order Douglas–Kroll–Hess (DKH) Hamiltonian44 with the corresponding full electron wDZ/wTZ basis sets. Most of the calculated corrections are below 1 kcal/mol, with the only one exception of 2.7 kcal/mol for singlet-quintet spin gap (Figure S7), indicating that we can safely omit Co 3s3p core-valence correlation and scalar relativistic effects in our calculations. Concerning the accuracy of CCSD(T) approach and its local variants like DLPNO-CCSD(T) for systems containing first-row transition metals, it is notable that there are still some uncertainties. Our calibration on reaction energy/barrier of small low-valent nickel systems,45 as well as the work of other groups on heats of formation and bond dissociation energies, indicate that CCSD(T) should be reliable for first-row transition metals.46 But there is also different opinion,47 which certainly calls for more calibration studies in future. Finally, we note that in the current Co(III) systems, DFT (B3LYP) results with DFT-D3 correction are generally quite close to the DLPNO-CCSD(T) results (Figures S1-S3). 3. RESULTS AND DISCUSSION To investigate the C-H activation reactivity of various spin states of Co(III), three typical systems shown in Scheme 1 were chosen, including both C(sp2)-H and C(sp3)-H activations, and covering Cp-Co(III) and non-Cp-Co(III) type catalysts. With these reaction systems, we focus on the commonly accepted concerted metalation-deprotonation (CMD) mechanism48 for Co(III)promoted C-H activations. For C(sp2)-H activations but not for C(sp3)-H activations, in addition to CMD mechanism, intermolecular or intramolecular single electron transfer (SET) mechanism was alternatively proposed,6b,9a,c,d,f,g,12d,18a which has been carefully explored in a previous DFT study.9d The scope of the current work is not to determine the mechanism of Co(III)-promoted C-H activation that is still under active debate, but to generally explore the multiple spin states of Co(III) within CMD mechanism at high computational level. In addition, SET mechanism has been ruled out in experiment for C(sp3)-H activations.5 Thus, we focus on CMD mechanism in the current work and the SET mechanism is not under study. To properly deal with the challenging issue of multiple spin states of Co(III), domain-based local pair natural orbital coupled cluster method (DLPNO-CCSD(T)) at the complete basis set (CBS) limit extrapolation level34 was employed to systematically investigate the key C-H activation processes in the three systems shown in Scheme 1. Below we start to present our key results for these three systems separately. The CMD reaction pathway from our DLPNO-CCSD(T) calculations for the C(sp2)-H activation of non-Cp-Co(III) system reported by Daugulis et al.,4a is depicted in Figure 1. All three possible spin states of Co(III) were investigated, i.e., the low-spin singlet (S = 0), medium-spin triplet (S = 1), and high-spin quintet (S = 2) states. Singlet and triplet states are quite close in energy for the reactant complex A, and are significantly less stable than the ground quintet state by ca. 10 kcal/mol. Of note is that for quintet state 5A, there is large spin population on the amidoquinoline bidentate directing group (Table S5), which means that this state is actually from quartet Co(II) ferromagnetically coupled
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with a ligand radical. The three states maintain the energy order of 5 A < 1A < 3A, with the high-spin ground state 5A lying below the singlet and triplet states by 10.2 and 11.6 kcal/mol, respectively. The C-H activation transition states TSAB, however, exhibit a permuted energy ordering of 1TSAB < 3TSAB < 5TSAB, with lowspin lying apparently lower than the medium-spin and high-spin states. This result indicates that along the reaction coordinate through TSAB on potential energy surface (PES), low-spin state is much more stabilized relative to the high-spin quintet state. This stabilization leads to intrinsic C-H activation barrier of only 13.6 kcal/mol on the singlet PES from 1A via 1TSAB.49 This barrier is much smaller compared to the corresponding intrinsic barrier of 35.1 kcal/mol on the high-spin quintet PES. It is notable that the relative energy of C-H activation product 5B is much higher than 3 B and 1B, leading to larger reaction energy of the quintet state. These significantly higher barrier and reaction energy together imply that the C(sp2)-H activation reaction on high-spin quintet state is both kinetically and thermodynamically much less favorable than the other two spin states.
TSAB (singlet). In this MSR scenario, the low-spin and mediumspin states, which are initially excited states, cross over the highspin ground state and promote C-H bond cleavage, the spin changes for which are expected to occur rapidly.
Figure 2. Optimized reactant and product structures in C(sp2)-H and C(sp3)-H activations by non-Cp-Co(III) type catalysts.
Figure 1. DLPNO-CCSD(T) calculated reaction profile of C(sp2)-H activation promoted by non-Cp-Co(III) type catalyst for the reaction shown in Scheme 1a.
It is unusual to get low-lying non-singlet states for Co(III) species A and B in octahedral coordination environment. However, it should be noted that ground spin state of Co(III) is dependent on the coordination environment. Previous experimental results have shown examples of non-singlet ground states for coordinatively unsaturated four- and five-coordinated Co(III).50 With acetate acting as bidentate ligand for reactant, the systems under study are less coordinatively saturate, since the occupation of the two empty coordinate sites by one acetate ligand is less complete than two monodentate ligands. In addition, the coordination of cobalt with acetate ligand is weaker for the out-of-plane Co-O bondings, as shown in Figure 2. Therefore, in this distorted six-coordinate environment with coordinatively unsaturated character, non-singlet spin states can possibly be ground state in the systems under study. It should also be noted that we still do not have enough knowledge about the accuracy of the DLPNO-CCSD(T) on the challenging spin gap issue of first-row transition metals. From the quintet ground state reactant 5A, the lowest effective barrier of C-H activation is 23.8 kcal/mol via the singlet 1TSAB, which can be compared with 28.7 and 35.1 kcal/mol respectively via triplet 3TSAB and quintet 5TSAB. Since triplet state barrier is only about 3-4 kcal/mol larger than the most favorable singlet state one, its involvement in the C-H activation cannot be safely excluded. For the singlet and triplet states, their corresponding calculated H/D kinetic isotope effect (KIE) values of 4.0 and 3.6 are relatively close, implying that it is difficult to use KIE to probe the reactive spin state involved in the reaction. Therefore, the reaction picture of the C(sp2)-H activation by non-Cp-Co(III) catalyst has the characteristics of MSR scenario, which involves all three spin states of Co(III) from A (quintet) to B (triplet) via
Figure 3. DLPNO-CCSD(T) calculated reaction profile of C(sp3)H activation promoted by non-Cp-Co(III) type catalyst for the reaction shown in Scheme 1b. For the C(sp3)-H activation of non-Cp-Co(III) system reported by Ge et al.,5 the DLPNO-CCSD(T) results shown in Figure 3 are qualitatively similar to C(sp2)-H case in Figure 1. First, the quintet state keeps to be the ground state of C-H activation reactant C, with the singlet/triplet state lying 6.6/8.8 kcal/mol above. It is notable that similar to 5A, the electronic structure of 5C is also from quartet Co(II) ferromagnetically coupled with the amidoquinoline ligand radical (Table S5). Along the reaction coordinate to the C-H activation transition state TSCD, the singlet state changes to be the lowest lying one, with triplet 3TSCD lying higher above singlet 1TSCD by 3.9 kcal/mol. The quintet 5TSCD, however, is much higher than singlet 1TSCD by about 13.5 kcal/mol, which indicates that 5TSCD is not likely to be involved in C(sp3)-H activation. At the product side, triplet state 3B is apparently lowest one, in contrast to the quintet ground state of reactant side. This reactivity picture is typically a MSR scenario, involving all thee spin states of Co(III). Similar to above C(sp2)-H activation, here the calculated H/D KIE values for C(sp3)-H activation are also very close (3.3 and 3.4) for singlet and triplet states, causing difficulty to use KIE as a probe for the spin state involved in the reac-
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tion. The calculated KIE data are in reasonable agreement with the experimental value (2.3).5 Despite having similar KIEs for CH activation on triplet and singlet states, since the ground quintet states of reactants (5A and 5C) are actually of Co(II) center ferromagnetically coupled with the amidoquinoline ligand radical, it could be possible to use the EPR spectroscopy to identify this spin state for probing MSR.
Figure 4. The crucial σCH-dz2(Co) orbital interaction in 1TSAB. The lowest effective C-H activation barrier measured from the ground state reactant 5C is 24.3 kcal/mol via singlet state 1TSCD. This larger effective barrier, as well as larger intrinsic C-H activation barrier of 17.7 kcal/mol, when compared with the corresponding effective/intrinsic barrier of 23.8/13.6 kcal/mol from C(sp2)-H activation in Figure 1, are in line with the chemical intuition that C(sp3)-H bond is more difficult to activate than C(sp2)-H bond. Interestingly, the C(sp3)-H activation reaction is more exothermic than C(sp2)-H activation reaction, especially for the triplet state. These results clearly demonstrate that it is kinetic factor rather than the reaction thermodynamic driving force that accounts for the inertness of C(sp3)-H activation. Notably, the higher reactivity of low-spin (singlet) state over high-spin (quintet) and medium-spin (triplet) state is the same feature shared by C(sp2)-H and C(sp3)-H activations with the non-Cp-Co(III) type catalyst. In Figure 4 we provide an orbital interaction scheme, which can explain why the singlet state is preferred to render the low-lying C-H CMD transition state for singlet. The empty dz2 orbital of singlet Co(III) is crucial to stabilize the C-H σ bond under activation, which is similar to the previous study on Fe(II) also with d6 configuration.32 Then, what about the Cp-Co(III) type catalyst?
Figure 5. DLPNO-CCSD(T) calculated reaction profile of C(sp2)H activation promoted by Cp-Co(III) type catalyst for the reaction shown in Scheme 1c.
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The DLPNO-CCSD(T)-calculated CMD reaction pathway for the C(sp2)-H activation by Cp-Co(III) type catalyst reported by Kanai et al.,3d is depicted in Figure 5. Different from the non-CpCo(III) type catalyst cases, here the three spin states are completely separated in energy along all the C-H activation reaction profile. Owing to strong ligand field of Cp ligand to stabilize the closedshell singlet state, the low-spin singlet state stays lowest, having the C-H activation barrier of 20.7 kcal/mol through transition state 1 TSEF. The prohibitively high relative energies of triplet and quintet transition states (32.0/42.0 kcal/mol for 3TSEF/5TSEF) imply that these two spin states are not accessible in the reaction (for quintet state profile from 5E to 5F via 5TSEF, there keeps large spin population on the Cp ligand (Table S5), which indicates that this state is actually from quartet Co(II) ferromagnetically coupled with a ligand radical). Therefore, the C(sp2)-H activation by CpCo(III) type catalyst with Cp ligand is featured by a single-state reactivity (SSR). This SSR validates the consideration of only the singlet state in previous theoretical study for C-H activation by Cp-Co(III) type catalysts.8b-d,9d,10g,11c,d Of note is that for CpCo(III) type catalyst the reaction energies on singlet and triplet states are both shifted to endothermic direction compared to that for non-Cp-Co(III) type catalyst, reducing the C-H activation reactivity of these two spin states thermodynamically. Correspondingly, the barriers on singlet/triplet states are higher for CpCo(III) type catalyst than that for non-Cp-Co(III) type catalyst (20.7/29.8 vs. 13.6/17.1 kcal/mol), which indicates that Cp ligand reduces the intrinsic C-H activation reactivity of singlet and triplet states. However, since MSR exists in non-Cp-Co(III) type catalyst, its effective barrier (23.8 kcal/mol) via the singlet 1TSAB from the quintet ground state reactant 5A is even larger than that (20.7 kcal/mol) in Cp-Co(III) type catalyst involving SSR only, which causes the lower C-H activation reactivity of the former case. Interestingly, inspecting the reverse processes of the C-H activations in Figures 1-3, it is clear that with relatively low barriers of 12.3 and 17.1 kcal/mol and being exothermic from B/F back to A/E, C(sp2)-H activations promoted by either Cp-Co(III) or nonCp-Co(III) type catalysts are reversible; while by bearing a higher barrier of 25.8 kcal/mol from D back to C and being endothermic, C(sp3)-H activation is much less reversible. This finding is fully consistent with the unexceptional experimental results to support the irreversible C(sp3)-H activations promoted by Co(III),5,8a,b,e lending more credence to the current high-level DLPNO-CCSD(T) calculations. Above results for three different Co(III)-promoted C-H activation systems demonstrate that variant MSR and SSR scenarios can be involved in the C-H activation mechanism, depending on the ligand of Co(III). In particular, these results imply that considering only the singlet state, as done in most previous theoretical studies on Co(III)-promoted C-H activations,6g,8b-d,i,9d,10g,11ce,q,12a,b,18y,26g is enough only for Cp-Co(III) type catalysts, but may not be adequate for non-Cp-Co(III) type catalysts. In general, the low-spin singlet state is most important to render energetically more accessible reaction channel for C-H activations by non-CpCo(III) type catalysts. This result is in agreement with our recent finding of Fe(III)/Fe(II)-promoted C-H activations, wherein lowspin state similarly plays this important role.32 The current finding of ligand-dependent MSR in C-H activation, combined with our recent finding of substrate-dependent TSR in C-C coupling of iron-promoted alkene [2+2] cycloaddition,51 show the possibility of modulation of MSR/TSR/SSR by factors such as ligand and substrate. 4. CONCLUSIONS In summary, using high level DLPNO-CCSD(T) method combined with DFT method, we have explored the roles played by all three
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spin states in several typical Co(III)-promoted C-H activation processes. Our results demonstrate that MSR involving three spin states operates for C-H activations with non-Cp-Co(III) type catalyst, while SSR involving only singlet spin state operates for C-H activation with Cp-Co(III) type catalyst. To our best knowledge, this work constitutes the first example to go beyond the commonly used DFT methods in modeling the reactivity of Co(III)promoted C-H activations. The unprecedented finding of liganddependent reaction scenario of MSR/SSR, together with the previous alternative SET mechanistic proposal for C(sp2)-H activation,6b,9a,c,d,f,g,12d,18a show the high complexity of the mechanism of Co(III)-promoted C-H activations, which certainly call for more theoretical and experimental efforts to gain deeper mechanistic insight.
ASSOCIATED CONTENT Supporting Information Calculated absolute energies and reaction profiles, calculated spin density populations, T1 Diagnostics for the DLPNO-CCSD(T) calculations, Cartesian coordinates of all the optimized structures. This material is available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION Corresponding Author
[email protected] ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (NSFC, Nos. 21873103, 21833011, and 21473215), and Institute of Chemistry, Chinese Academy of Sciences.
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with Currently Available Functionals When Compared to the Best Available Experimental Data for Dissociation Energies of Bonds to 3d Transition Metals? J. Chem. Theory Comput. 2015, 11, 2036–2052. (48) (a) Biswas, B,; Sugimoto, M.; Sakaki, S. C-H Bond Activation of Benzene and Methane by M(η2-O2CH)2 (M = Pd or Pt). A Theoretical Study. Organometallics 2000, 19, 3895–3908. (b) Davies, D. L.; Donald, S. M. A.; Macgregor, S. A. Computational Study of the Mechanism of Cyclometalation by Palladium Acetate. J. Am. Chem. Soc. 2005, 127, 13754–13755. (c) Boutadla, Y.; Davies, D. L.; Macgregor, S. A.; Poblador-Bahamonde A. I. Mechanisms of C-H bond activation: rich synergy between computation and experiment. Dalton Trans. 2009, 5820–5831. (d) Gorelsky, S. I.; Lapointe, D.; Fagnou, K. Analysis of the Concerted Metalation-Deprotonation Mechanism in Palladium-Catalyzed Direct Arylation Across a Broad Range of Aromatic Substrates. J. Am. Chem. Soc.
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2008, 130, 10848–10849. (49) We note that the current DLPNO-CCSD(T)-calculated C-H activation barrier is significantly smaller than previous DFT result of similar non-Cp system (ref. 9d), which shows that DFT may overestimate this CH activation barrier on singlet state systematically. (50) (a) Brewer, J. C.; Collins, T. J.; Smith, M. R.; Santarsiero, B. D. Neutral Square Planar Cobalt(III) Complexes. J. Am. Chem. Soc. 1988, 110, 423–428. (b) Gennari, M.; Gerey, B.; Hall, N.; Pécaut, J.; Collomb, M.-N.; Rouzières, M.; Clérac, R.; Orio, M.; Duboc, C. A Bio-Inspired Switch Based on Cobalt(II) Disulfide/Cobalt(III) Thiolate Interconversion. Angew. Chem. Int. Ed. 2014, 53, 5318–5321. (51) Hu, L.; Chen, H. Substrate-Dependent Two-State Reactivity in Iron-Catalyzed Alkene [2+2] Cycloaddition Reactions. J. Am. Chem. Soc. 2017, 139, 15564–15567.
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