DFT Studies on the Dirhodium-Catalyzed [3 + 2] and [3 + 3

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DFT Studies on the Dirhodium-Catalyzed [3 + 2] and [3 + 3] Cycloaddition Reactions of Enol Diazoacetates with Isoquinolinium Methylide: Mechanism, Selectivity, and Ligand Effect Shi-Jun Li and De-Cai Fang* College of Chemistry, Beijing Normal University, Beijing 100875, People’s Republic of China S Supporting Information *

ABSTRACT: The reaction mechanisms of dirhodium-catalyzed [3 + 2] and [3 + 3] cycloaddition between enol diazoacetate and isoquinolinium methylide have been studied in detail using density functional theory and a solution-phase translational entropy model. The reaction starts with the formation of a metallic carbene intermediate first, from which two competing reaction channels of [3 + 2] and [3 + 3] cycloaddition take place. For CAT1-catalyzed reactions, the calculated activation free energy barriers for [3 + 3] and [3 + 2] cycloaddition reactions are 14.3 and 16.0 kcal mol−1, respectively, which is in good agreement with the ratio of products. Both the steric and electronic effects have been considered for CAT2- and CAT3-catalyzed reactions, with which the ratio of products has also been rationalized.

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INTRODUCTION Cycloaddition reactions, as powerful tools in organic chemistry, have been employed in chemistry, materials science, and biology.1 The mechanism studies of various cycloaddition reactions have always been a hot topic for experimentalists and theoreticians, and most of the traditional cycloaddition reactions are believed to be concerted processes.2,1b With the assistance of Lewis catalysts and metal catalysts, cycloaddition reactions have become more approachable. In addition, the stereoselectivity and enantioselectivity of the reactions have been more controllable.3 Among these, dirhodium-catalyzed cycloaddition reactions have received much attention, since almost all types of cycloaddition reactions, such as [2 + 1], [3 + 2], [3 + 3], [4 + 3], [5 + 1], [4 + 2], and [2 + 2 + 2], have been reported.3e,4 The first dirhodium compound was uncovered by Chernyaev et al. in their experiment,5 and the unique paddlewheel structure of dirhodium tetraacetate was verified by different research groups using X-ray diffraction.6 On the foundation of the pioneering works on synthesis and structure, a large number of dirhodium compounds have been synthesized by the replacement of acetate with different analogues, such as carboxamidates, phosphates, and others.4b,7 Since the dirhodium-catalyzed Merck synthesis of the antibiotic thienamycin via intramolecular N−H insertion of a diazoacetoacetate expanded the application of dirhodium compounds in chemistry,8 the popular dirhodium-catalyzed C−H/N−H activation and cycloaddition, S−H insertion, and aldol-type reactions have also been discovered.4b,9 Simultaneously, it has been revealed that the formed metallic carbene would be directly correlated with the products in these reactions.10 With © XXXX American Chemical Society

the assistance of chiral and achiral ligands, the utilization of dirhodium catalysis has been expanded to a large area, including natural product synthesis,11 materials science,4e,12 biology,13 and so on. There have been few theoretical studies on dirhodiumcatalyzed reactions before 2011,14 but recently the development has been quite rapid, and some typical examples are mentioned herein. In 2011, Hansen and coauthors reported a study on the dirhodium-catalyzed C−H activation/Cope rearrangement reaction by using the B3LYP method, indicating that metallic carbene might be important in the reaction.15 In 2012, Li et al. employed a simplified model (with HCOO− replacing the ligand) to study the mechanism of dirhodium-catalyzed tandem ylide formation and [2,3]-sigmatropic rearrangement by the M06L method, in order to explain the factors for controlling product branching ratio and to rationalize the diastereoseletivity of the reactions.16 Since 2013, Zhao’s group has studied dirhodium-catalyzed C−H activation, in order to rationalize the possible electronic processes and competing reaction channels.17 In 2014, Kisan et al. investigated the dirhodiumcatalyzed asymmetric amination of diazocetate using both M06 and B3LYP methods and explained the experimental selectivity.18 In 2015, Xue et al. studied a cyclopropanation reaction catalyzed by the achiral catalysts Rh2(OAc)4 and Rh2(S-PTTL)4 using the B3LYP-D3 method and found that the dirhodium catalyst could reduce the Gibbs free energy barriers and the chiral ligands in the dirhodium catalyst could affect the addition reactions.19 In 2016, the chemoselectivity20 Received: February 1, 2018

A

DOI: 10.1021/acs.organomet.8b00069 Organometallics XXXX, XXX, XXX−XXX

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Organometallics Scheme 1. Description of the Studied Reactions

of dirhodium-catalyzed [3 + 2] reactions was investigated by Xue’s group and the enantioselectivity21 of the C−H insertion reaction was investigated by Xie’s group with different DFT methods. In 2017, Wei et al. studied ring expansion reactions by using the B3PW91 method and found that the dirhodium nitrene intermediate is crucial for the reaction but not essential for controlling the selectivity.22 In the same year, Wang et al. reported the transannulation of pyridotriazole with phenylacetylene and benzonitrile and discussed the chemoselectivity in cyclization.23 As we know, general [3 + 3] cycloaddition without a catalyst is rare owing to the unstable structures of the reactive dipolar species,3d,e,24 but cooperation with organic and metal catalysts would help to form stable structures of the reactive dipolar species.25 In 2013, Xu et al. reported the competitive reactions [3 + 3] cycloaddition and [3 + 2] cycloaddition of enol diazoacetates and isoquinolinium methylides with dirhodium catalysts, shown in Scheme 1.26 After reaction in toluene solution at room temperature for 3 h, the main product of the Rh2(S-PTIL)4(CAT1)-catalyzed reaction was found to be that of [3 + 3] cycloaddition (P2). In contrast, the main product for Rh 2 (S-TCPTTL) 4 (CAT2)-catalyzed (after 3 h) and Rh2(CF3COO)4(CAT3)-catalyzed reactions (after 24 h) was confirmed to be that of [3 + 2] cycloaddition (P1). What is attractive to us is determination of how the dirhodium catalysts affect the reaction mechanisms and the catalyst ligand affects the ratio of products. Through theoretical studies, this determination would be beneficial for revealing the mechanism of dirhodium-catalyzed cycloaddition and understanding the dirhodium-catalyzed competing channels, which would provide a valuable reference for the design and development of dirhodium catalysts.

Figure 1. Three possible structures, relative energies, and Gibbs free energies (in kcal mol−1) for the isomers of CAT1 at room temperature.

The overall competing [3 + 2] and [3 + 3] cycloaddition reactions between the reactant enol diazoacetate R1 and the reactant isoquinolinium dicyanomethylide R2 catalyzed by catalyst Rh2(S-PTIL)4, denoted CAT1, are depicted in Scheme 2, from which one can realize that the common intermediate metallic carbene M1 is formed between R1 and CAT1 and then two different channels are observed after the introduction of R2. For the first pathway, cyclopropene M2 could be formed after a 1,3-addition and the departure of CAT1 from M1, and then a typical [3 + 2] cycloaddition process could take place Scheme 2. General Mechanism for CAT1-Catalyzed Competing Reactions from R1 and R2 to P1 and P2

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RESULTS AND DISCUSSION Mechanism. There are several different isomers of catalyst CAT1, among which the Fox model,27 the Hashimoto model,28 and a staggered model have been optimized by using B3LYPIDSCRF/DGDZVP as shown by isomers a−c in Figure 1, respectively. The generation of different isomers should be attributed to the chirality and orientation of the ligand S-PTIL (see Scheme 1) in the catalyst, and the stability of the different isomers is also related to the orientation of the ligand S-PTIL. Obviously, isomer a has been characterized as the most stable form in a thermodynamic aspect from the relative energy and Gibbs free energy, since isomers b and c lie ca. 4.3 and 6.3 kcal mol−1 above isomer a in relative Gibbs free energy, respectively. Therefore, isomer a has been chosen as CAT1 for further discussion. B

DOI: 10.1021/acs.organomet.8b00069 Organometallics XXXX, XXX, XXX−XXX

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15.9 kcal mol−1, which can easily proceed even at room temperature, and it will release a Gibbs free energy of 10.7 kcal mol−1. However, the activation free energy barrier for the formation of M1-II is 18.3 kcal mol−1, ca. 2.4 kcal mol−1 higher than that for mode I, which can be attributed to the greater steric repulsion between alkyl groups in the ligands and R1. The stabilities of the two intermediates are quite similar according to the results from B3LYP-IDSCRF/DGDZVP calculations, and thus only M1-I has been employed for the following discussions. Modern computational works have considered dispersion correction with empirical D3 for the reaction process; however, one should be cautious in applying this method to a bimolecular reaction process. The complexes COM1-I and COM1-II have been characterized to be very stable structures by using the B3LYP-IDSCRF+D3/DGDZVP method, with the stabilization energies being 35.8 and 23.9 kcal mol−1, which are clearly overestimated. The Rh(1)−C(2) bond distance in COM1-I is optimized to be 2.481 Å, only 0.014 Å shorter than that obtained with the B3LYP-IDSCRF/DGDZVP method, and the density ρb of Rh(1)−C(2) is only 0.045 au at the bond critical point for COM1-I, indicating only a weak interaction between CAT1 and R1 fragments. The Mulliken and NBO charge transfers (CTs) in COM1-I between CAT1 and R1 fragments are calculated to be 0.170 and 0.190 e, and thus this dominant CT process will not cause a large dispersion interaction. The present dispersion correction method has not considered the charge distribution change of the atomic interaction pairs for the different stationary points, and especially, the parameter of the atomic interaction pair between a transition-metal element and non-transition-metal element is not well established.29 For example, the complexed Gibbs free energy between CAT1 and acetonitrile is measured to be −3.0 kcal mol−1 from the equilibrium constant,26 which is quite close to our B3LYP-IDSCRF/DGDZVP result of −5.4 kcal mol−1. With D3 dispersion correction, it becomes −12.1 kcal mol−1, much more negative than the experimental measurement. In additional, this reaction process has also been examined by B3LYP-IDSCRF/BS1(SDD for Rh and DGDZVP for the other atoms), B3LYP-IDSCRF/def2TZVP, M06-IDSCRF/ DGDZVP, and ωB97X-IDSCRF/DGDZVP to find a suitable method for the system (see the Supporting Information). The results obtained with M06 and ωB97X are quite close, but the combination free energy between CAT1 and acetonitrile is obviously overestimated by more than 9.0 kcal mol−1. Since B3LYP-IDSCRF/DGDZVP gives the closest result to that found experimentally, the results obtained with this method will be employed in the following discussion. [3 + 2] Cycloaddition Process. As depicted in Figure 3, the intermediate M2 could be generated from the metallic carbene intermediate M1-I via the addition−dissociation transition state TS2; herein the catalyst CAT1 is recovered. In TS2, the Rh(1)−C(3) bond distance becomes 2.183 Å from 2.058 Å in M1-I, only a 0.125 Å bond distance change, but after TS2, the Rh(1)−C(3) bond distance changes dramatically according to our IRC calculations. However, the change in C(3)−C(5) bond distance is obvious from 2.424 Å in M1-I to 1.536 Å in M2 via 2.006 Å in TS2a, indicating that this is the main reaction coordinate for the transformation from M1-I to M2. The calculated bond length data along this reaction process indicate that the bonding pattern changes of C(3)−C(4) and C(4)−C(5) are also distinct, with the change of a partial double bond to a strong double bond for C(3)−C(4) and the change

between reactant R2 and M2. For the second pathway, a [3 + 3] cycloaddition reaction between intermediate M1 and reactant R2 can generate product P2 directly. Formation of Metallic Carbene Intermediate. Interestingly, there are two different activation sites along the Rh−Rh bond for the isomer, as shown in Figure 1, due to the asymmetric ligand S-PTIL for catalyst CAT1. According to the relative position of heterocycle and alkyl groups, one can define the site surrounded by heterocycles as the up site (mode I) and the other site surrounded by alkyls as the down site (mode II), the same as the relative position in Figure 1. Due to the orientation of ligands, the attacking space of mode I would be much bigger than that of mode II, which might influence the catalyzed reaction mechanisms and free energy profiles. First, the complex COM1-I in mode I will be generated after the mixture of reactant R1 and CAT1, leading to a Rh(1)− C(3) bond distance of 2.495 Å. The C(3)N(6) bond length elongates from 1.319 Å in R1 to 1.366 Å in COM1-I, and the bond length of N(6)N(7) slightly decreases from 1.140 Å in R1 to 1.126 Å in COM1-I. Along the proceeding pathway of the reaction, the Rh(1)−C(3) bond length will be changed from 2.209 Å in TS1-I to 2.058 Å in M1-I, and at the same time, the N(6)N(7) bond length will become 1.109 Å in TS1-I from 1.126 Å in COM1-I, the same as that in a free N2 molecule, indicating the formation of metallic carbene M1-I after the release of gaseous product N2. For mode II, the Rh(2)−C(3) bonding lengths in all of the stationary points are slightly longer than those in mode I, due to the greater steric repulsion between alkyl groups in ligands and R1 for this mode. The energy profiles for these two modes are depicted in Figure 2, from which one can observe that the formation of COM1-I will release electronic energy of 2.8 kcal mol−1 but increase the Gibbs free energy by ca. 7.9 kcal mol−1, which originates from the change in entropy from two molecules to one molecule. The formation of the metallic carbene intermediate M1-I needs to overcome a free energy barrier of

Figure 2. Formation of metallic carbene intermediate M1-I/II. Herein I represents the upside R1 approaching mode and II stands for the downside R1 approaching mode (bond lengths in Å, relative energy and free energy at 298.15 K in kcal mol−1). C

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Figure 3. Relative energy and Gibbs free energy profiles (in kcal mol−1), along with some key geometric structures and parameters (in Å) for the [3 + 2] process.

Figure 4. Schematic diagram of frontier orbitals for M2, R2, TS3endo/exo-a, and TS3-endo/exo-b, energies of frontier orbitals (eV) for M2 and R2, and NBO charges (in green) for the M2 part in the transition state.

of a double bond to a typical single bond for C(4)−C(5). The calculated activation free energy barrier is ca. 6.5 kcal mol−1, close to the activation electronic energy barrier of ca.7.4 kcal mol−1. The formation of M2 will release a Gibbs free energy of 6.3 kcal mol−1, which shows that the M2 would be more stable than the intermediate M1-I. For [3 + 2] cycloaddition reactions between M2 and R2, there are four approaching modes, i.e., exo-a, exo-b, endo-a, and endo-b, as indicated in Figure 3. In addition, it can be seen that four corresponding products have been formed via four different transition states. The C(3)−C(10) and C(4)−C(8) bond distances in TS3exo-a and TS3-endo-a are calculated to be 2.155, 2.533 Å and 2.206, 2.439 Å, respectively, indicating that they are the result of a concerted but asynchronous process. In addition, the C(4)−C(10) and C(3)−C(8) bond distances in TS3-exo-b and TS3-endo-b are 2.172, 2.469 Å and 2.117, 2.481 Å. The C(3)− C(4) length increases by ca. 0.066 Å for both TS3-exo-a and TS3-endo-a but by ca. 0.060 Å for TS3-exo-b and TS3-endo-b, indicating that there is a transformation from the original double bond to a single bond. According to the experimental procedure,26 a mixture of CAT1 and R2 dissolved in toluene solvent was stirred for 5 min before R1 toluene solution was added via syringe pump over 1 h, meaning that M2 would react with R2 immediately once it was formed. Since the accumulation of concentration for M2 could be treated as zero, the steady-state approximation30 should be valid here, meaning that the Gibbs free energy barrier could be counted as the difference between the transition state (different TS3s) and M1-I+R2. The calculated activation free energy barriers for exo-a, endo-a, exo-b, and endo-b modes are 18.6, 16.0, 22.6, and 24.3 kcal mol−1, respectively, among which the endo-a mode is the most kinetically favorable. The stereoselectivity of the cycloaddition could be explained with two pairs of frontier orbital (FMO) interactions: the HOMO of M2 and LUMO of R2 and the HOMO of R2 and LUMO of M2, as shown in Figure 4. It can be realized from Figure 4 that the dominant FMO interaction for stabilizing TS3-exo-a and TS3-endo-a is that between the HOMO of M2

and the LUMO of R2 from the electron transfer direction, while the main FMO interaction to stabilize TS3-exo-b and TS3-endo-b is that between the HOMO of R2 and LUMO of M2. The energy gap for the former FMO interaction is only 3.8 eV, 0.9 eV lower than the latter FMO interaction, leading to the approaching modes of exo-a and endo-a being more favorable than those of exo-b and endo-b. [3 + 3] Cycloaddition. Apart from the [3 + 2] cycloaddition reaction, the intermediate M1-I could react directly with reactant R2 in the Re face approaching mode and Si face approaching mode via a [3 + 3] cycloaddition process, as shown in Scheme 3, to generate products P2-S and P2-R, respectively. The orientation of the prochiral hydrogen atom H11 in R2 would determine the Re face approach and Si face approach to M1-I and thus lead to the corresponding products. For the process from M1-I to P2-S/R, three geometric parameters, Rh(1)−C(3), C(3)−C(10), and C(5)−C(8), are defined as the main reaction coordinates, but they change dramatically in different stages. For example, the C(5)−C(8) bond distance changes from 3.093 Å in TS4-S to 1.600 Å in M3-S, and thus a typical single C−C bond is formed in this intermediate; subsequently, the formation of C(3)−C(10) takes place mainly after the intermediate M3-S, which is evident from the change (3.091−1.537 Å) in this bond distance along M3-S, TS5-S ,and P2-S. The bond length change of Rh(1)− C(3) from M1-I to M3-S is only 0.123 Å (2.058−2.181 Å), but it increases to 2.410 Å in TS5-S. A similar trend has been observed for the Re face approach mode. The energy and free energy profiles for the Re face approach mode and Si face approach mode are quite different, as shown in Figure 5. Since the concentration accumulation of M3-S and M3-R could be regarded as zero, the steady-state approximation should be valid here. Therefore, the free energy barrier of the Si face approach mode could be counted as the free energy difference between TS4-S and M1-I+R2, while that for the Re D

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a

Bond lengths are given in Å.

been chosen to further illustrate this effect, and it is denoted CAT2, as illustrated in Scheme 1. Even though the structure of CAT2 is quite similar to that of CAT1, the product selectivity is totally different from that found in experiments.23 Experimental measurements demonstrated that the main product for the CAT1-catalyzed reaction is P2-S, while the main product for the CAT2-catalyzed reaction is the [3 + 2] cycloaddition product P1-endo-a. The whole Gibbs free energy profile for CAT2-catalyzed [3 + 2] and [3 + 3] cycloaddition reactions is depicted in Figure 6,

Figure 5. Gibbs free energy and energy profiles for the [3 + 3] process (in kcal mol−1) and schematic diagrams for steric obstruction in TS5-S and TS5-R.

face approach mode could be calculated as the free energy difference between TS5-S and M1-I+R2. It is obvious that the Si face approach mode could play a dominant role in this [3 + 3] process since the calculated free energy barriers at room temperature for the Re face approach mode and Si face approach mode are 14.3 and 21.5 kcal mol−1, respectively. The greater steric repulsion between the aryl group in R2 and ligands in CAT1 fragment for Re face approach could be realized from the data for the mainframe torsional angle OCCN for Re face approach and Si face approach (51.2 vs 151.0°). The process is kinetically controlled, although the product P2-R is ca. 3.0 kcal mol−1 more stable in free energy at room temperature than the product P2-S. Ligand Effect of the Catalysts. Steric Effect. In the previous section, we have discussed the [3 + 2] and [3 + 3] reaction pathways and the way the ligands in CAT1 would affect the [3 + 3] reaction for a second reactant approach mode. In this section, a more crowded catalyst, Rh2(S-TCPTTL)4, has

Figure 6. Free energy profiles (298.15K) for [3 + 2] and [3 + 3] reaction channels catalyzed with CAT1 (in blue) and CAT2 (in red).

along with that for CAT1-catalyzed reactions discussed in the previous section. Since the formation process of metallic carbene is not obviously related to the ratio of the products, detailed information about this process can be found in the Supporting Information. The relative free energies of the transition states for the CAT2-catalyzed [3 + 3] cycloaddition E

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Figure 7. Steric repulsion between the ligands in CAT1 and CAT2 fragments on TS4-S and TS4-2-S.

favors the process M2-3+R1 → M1-3+M2+N2, thus bringing the whole free energy profile down. It can be seen from Figure 8 that the relative free energy of TS3-1+M2 is ca. 1.1 kcal mol−1 higher than that of TS4-3-S, indicating that the product P2-S will become dominant. However, the generated P2-S might react with CAT3 again to make the original [3 + 3] reaction reversible, since the reaction took place in 24 h in the real experiment, much longer than the times for CAT1- and CAT2-catalyzed reactions (3 h). Hence, the thermodynamically stable P1-endo-a would become the dominant species after a longer reaction time. In order to investigate whether or not the steric repulsion would be still the key factor in CAT3-catalyzed reactions, we have also conducted the characterization of pseudo-CAT4catalyzed reactions, in which the 12 fluorine atoms in CAT3 are replaced with 12 hydrogen atoms. The metallic carbene M1-4 formed could undergo a 1,3-addition reaction to release CAT4, and the second R1 could not attach to the second Rh in CAT4, and thus the reaction proceeds in the same way as CAT1- and CAT2-catalyzed reactions, which means that the electronattracting effect of four CF3 groups in CAT3 might also play an important role in the formation of the [3 + 2] product. For CAT4-catalyzed reactions, the main product should be P2-S, because the activation free energy barrier for the reverse process is 33.7 kcal mol−1, clearly not reversible at room temperature. It can be realized that the simplified model of ligands might not be suitable for the present system. A detailed description can be found in the Supporting Information.

process are all higher than those for the CAT1-catalyzed reactions, which is in the same trend as the size of ligands in catalysts CAT2 and CAT1 (see Figure 7). It is worth noting that the larger ligands in CAT2 could increase the relative Gibbs free energy of TS4-2-S obviously, since the introduction of R2 will cause more steric repulsion of the original ligands in CAT2 (see Figure 7b). The relative free energy to CAT2+R1+R2 of TS4-2-S is ca. 1.9 kcal mol−1 higher than that of TS3-endo-a, indicating that P1-endo-a is the main product for CAT2-catalyzed reactions. However, the relative free energy to CAT1+R1+R2 of TS4-S is ca. 1.7 kcal mol−1 lower than that of TS3-endo-a, leading to P2-S possibly being the main product for CAT1-catalyzed reactions, which is in good agreement with experimental measurements. Electronic Effect. For the CAT3-catalyzed reactions, the mechanism of [3 + 2] cycloaddition reaction is quite different from those for CAT1- and CAT2-catalyzed reactions. The 1,3addition reaction would not break the C−Rh bond, since the ligand in CAT3 is quite small and the electron-withdrawing ability of the ligand CF3COO is strong. Herein, the relatively stable intermediate M2-3 is formed, with the C−Rh bond length being 2.280 Å. Owing to the different properties of CAT3, s second R1 could approach a second Rh atom to form the complex COM2-3, which helps M2 to be separated from M2-3 (see Figure 8). Because of the release of gaseous N2 from the reaction solution, the translational entropy of gaseous N2

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CONCLUSION The mechanisms of cycloaddition reactions catalyzed by the three dirhodium catalysts CAT1, CAT2, and CAT3 between enol diazoacetates and isoquinolinium methylide have been investigated with a DFT method, from which the following conclusions can be made. (1) For CAT1-catalyzed reactions, the calculated activation free energy barriers for both reaction channels reveal that the [3 + 3] product is the dominant one. (2) For CAT2-catalyzed reactions, the larger steric repulsions within the ligands in the catalyst lead to the [3 + 2] main product. (3) For CAT3-catalyzed reactions, the strong electronattracting ability of ligands causes the different [3 + 2] cycloaddition mechanism, and the reversible [3 + 3] cycloaddition reaction might result in the main product of a [3 + 2] cycloaddition reaction.

Figure 8. Gibbs free energy profile for CAT3- and CAT4-catalyzed reactions, along with some key structures (bond lengths in Å). F

DOI: 10.1021/acs.organomet.8b00069 Organometallics XXXX, XXX, XXX−XXX

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All theoretical calculations in this study were performed with the Gaussian 09 program package.31 All structures of reactants, transition states, intermediates, and products were optimized using the Becke-3− Lee−Yang−Parr,32 in conjunction with the DGDZVP basis set.33 The self-consistent reaction field (SCRF) polarizable continuum model (PCM)34 with our recently established IDSRCF radii35 was also applied to simulate the solvent effect, in which toluene was employed as solvent, methodologically abbreviated as B3LYP-IDSCRF/ DGDZVP. This solvation model has been successfully applied to transition-metal-catalyzed C−H activations36 and cycloadditions.3a All of the optimized stationary points have been identified as minima (zero imaginary frequencies) or transition states (one imaginary frequency), via the vibrational analyses at the same level. In addition, intrinsic reaction coordinate (IRC) computations with Hessian-based predictor−corrector integrator (HPC)37 have been used to test some reaction steps to confirm the located transition states as residing on the correct reaction coordinates. Furthermore, the single-point energy calculations for other functional methods, for example, M06-IDSCRF/ DGDZVP38 and ωB97X-IDSCRF/DGDZVP,39 have been performed for the comparison of DFT methods, and other two basis sets, BS1(SDD40 for Rh and DGDZVP for other atoms) and def2TZVP,41 have also been employed for a comparison of the optimized structures and relative free energies by using the B3LYP-IDSCRF method. The solution translational entropy correction has been calculated with our THERMO program,42 which is based on the free volume that a solute molecule could move along three axes within the cavity. A D3 model of dispersion correction29a has also been considered for comparison. For some structures, the electron density at the bond critical point, ρb, on the basis of the atoms-in-molecules (AIM) theory,43 has been analyzed with the wave functions generated from the B3LYP-IDSCRF/DGDZVP calculations.

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.8b00069. Vibrational frequencies, electronic energies, Gibbs free energies, entropies, and complementary mechanistic characterizations (PDF) Optimized Cartesian coordinates for all stationary points (XYZ)

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AUTHOR INFORMATION

Corresponding Author

*E-mail for D.-C.F.: [email protected]. ORCID

Shi-Jun Li: 0000-0001-9872-6245 De-Cai Fang: 0000-0003-3922-7221 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Nature Science Foundation of China (21773010). REFERENCES

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DOI: 10.1021/acs.organomet.8b00069 Organometallics XXXX, XXX, XXX−XXX