The Concept of Protobranching and Its Many Paradigm Shifting

Feb 15, 2010 - is not realized that the only way to eValuate the strain energy is to employ a .... g ) [ 1 0. 0 1. -3 3]. | 1 0 C2H6. 0 1 C3H8. -3 3 C...
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J. Phys. Chem. A 2010, 114, 3731–3736

Comment on “The Concept of Protobranching and Its Many Paradigm Shifting Implications for Energy Evaluations” Ilie Fishtik Department of Chemistry and Biochemistry, Worcester Polytechnic Institute, Worcester, Massachusetts 01609 ReceiVed: September 14, 2009; ReVised Manuscript ReceiVed: October 27, 2009 In any organic chemistry textbook it is stated that the strain energy of cyclopropane is 27.5 kcal/mol. Recently, Schleyer et al.1 argued that the strain energies of cyclopropane should be 8.5 kcal/mol less than the conventional value. Their considerations are based on the concept of protobranching, i.e., a specific type of 1,3-alkyl-alkyl interaction present in any alkane except methane and ethane. It is further concluded that the conventional strain energy evaluations do not properly balance the number of protobranches and, therefore, should be revised. Schleyer et al.’s definition of a protobranch postulates that in cyclopropane “no protobranching 1,3alkyl-alkyl interactions are present since all carbon atoms are directly bonded to one another”. Similarly, according to Schleyer et al.1 there are only two protobranches in cyclobutane. In the meantime, the C-C-C groups or interactions are not new. As mentioned by Schleyer et al., Allen2 was the first to introduce the C-C-C groups in group additivity schemes. More recently, the C-C-C groups were incorporated into a group additivity model by Gronert.3 Within the group additivity approach the nature of interaction between the terminal carbon atoms in the C-C-C group is irrelevant. What counts is the number of these structural units. Thus, according to the group additivity formalism, cyclopropane involves three C-C-C groups as illustrated below

while cyclobutane involves four C-C-C groups

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carbon atoms chemically interact is not valid since it is this interaction that is the source of strain! In our opinion, the confusion regarding the “new” concept of protobranching is mainly due to a lack of understanding of how the strain energy, or any other energy evaluation, such as resonance energy, is defined and evaluated. First, it is not realized that the only way to eValuate the strain energy is to employ a group additiVity method. Namely, the strain energy of a species represents the difference between the enthalpy of formation calculated via a group additivity scheme and the experimental enthalpy of formation. Second, it is not understood that strain energy evaluations based on single reaction schemes and group additivity methods are intimately interrelated. This interrelation has been recently revealed by showing that that the group additivity methods can be equivalently reformulated in terms of a special class of reaction schemes referred to as group additivity reactions.4 In view of this result, the evaluation of the strain energy based on a single reaction scheme is nothing but a particular case of the general group additivity method. As is wellknown, group additivity methods usually involve a large number of reference species. This is equivalent to millions of reaction schemes. In contrast, a single reaction scheme method is based on a minimal number of reference species where by “minimal” it is meant that removing one of the reference species there is no way to write a balanced reaction scheme involving only the remaining species. As a result, the strain energy evaluations based on a single reaction scheme are always inferior as compared to group additivity methods in that a particular reaction scheme is just one from an enormous number of reaction schemes implicitly considered by a group additivity method. In this respect a special remark needs to be made for methane as a reference species. If methane is not used as a reference species in group additivity methods, it should neither be used in any reaction schemes. It is unanimously accepted that alkanes are the natural reference species for the evaluation of strain energies of hydrocarbons. Since methane is ruled out by any group additivity method for alkanes, it is fundamentally wrong to employ methane as a reference species in eValuating the strain energy of cycloalkanes. In particular, the strain energy of cyclopropane evaluated by Schleyer et al. via the isodesmic reaction

C3H6 + 3CH4 ) 3C2H6

∆H ) -19.29 kcal/mol

(2) Hence, from a group additivity point of view, the conventional reaction scheme

C3H6 + 3C3H6 ) 3C3H8

∆H ) -27.7 kcal/mol

(1) that is a measure of the strain energy in cyclopropane perfectly balances the number of C-C-C groups. If so, the crucial problem with protobranching is to what extent the C-C-C groups in cyclopropane differ from protobranches? The Schleyer et al.’s argument that in cyclopropane the groups C-C-C are not protobranches because the terminal

is flawed because this reaction balances only the number of C-H and C-C bonds. As is well-known, the principle of bond additivity is simply not valid. In this Comment we present a detailed quantitative analysis of the strain energy in an attempt to prove the above statements. Single Reaction Schemes We start with showing that any single reaction scheme used to evaluate the strain energy is the stoichiometric expression of a certain group additivity method. Benson Model. Consider the evaluation of the strain energy of cyclopropane assuming that the list of reference species

10.1021/jp908894q  2010 American Chemical Society Published on Web 02/15/2010

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includes a minimal number of species (two), namely, ethane and propane. Consider, first, the classical Benson model.5 For the three species under consideration, i.e., ethane, propane, and cyclopropane, we have only two types of Benson groups, i.e., g1 ) CH3 and g2 ) CH2 and, thus, the group additivity matrix is

Comments

|

|

1 0 C2H6 0 1 C3H8 ) 3C2H6 - 3C3H8 + C3H6 ) 0 -3 3 C3H6

or

C3H6 + 3C2H6 ) 3C3H8

Let the group contributions for g1 and g2 be H1 and H2. According to the group additivity formalism the group contributions may be determined from the following system of linear equations

2H1 ) ∆f H 0(C2H6) ) -20.04 kcal/mol 2H1 + H2 ) ∆f H 0(C3H8) ) -25.02 kcal/mol

∆H ) -27.7 kcal/mol

Thus, eq 1 that is the conventional measure of the strain energy of cyclopropane represents the stoichiometric expression of the Benson group additivity model. As such, eq 1 is valid independently on the way we count the protobranches. Clearly, stating that eq 1 is wrong would immediately imply that the Benson model is wrong. Equivalence of Group Additivity Models. Next, we show that various group additivity models are equivalent in that they possess the same stoichiometric expressions and, consequently, predict the same strain energy. As an example, consider the Allen2 group additivity model. For the two reference species model we have a total of three groups, namely, g1 ) C-H, g2 ) C-C, and g3 ) C-C-C. The group matrix is thus

Solving this system of linear equations gives

H1 ) 1/2∆f H 0(C2H6) ) -10.02 kcal/mol H2 ) ∆f H 0(C3H8) - ∆f H 0(C2H6) ) -4.98 kcal/mol Now, we can estimate the enthalpy of formation of cyclopropane via the group additivity scheme

∆f H GA(C3H6) ) 3H2 ) 3∆f H 0(C3H8) - 3∆f H 0(C2H6) ) -4.98 kcal/mol By definition, the strain energy is

∆H ) ∆f H GA(C3H6) - ∆f H 0(C3H6) ) 3∆f H 0(C3H8) - 3∆f H 0(C2H6) ∆f H 0(C3H6) ) -27.68 kcal/mol As can be seen, the strain energy of cyclopropane represents the enthalpy change of the reaction scheme given by eq 1. An alternative and equivalent way to solve the same problem is to directly generate a reaction scheme starting from the group matrix.4 In doing this, it is convenient to perform a series of elementary row operations to transposed group matrix and bring it to an echelon form

g)

[ ] 1 0 0 1 -3 3

The rank of the group matrix is equal to q ) 2 and, hence, according to the group additivity response reactions (RERs) formalism4 any q + 1 ) 2 + 1 ) 3 species define a RER. It means that for our system there is only one RER and this is given by

Observe that the number of g3 ) C-C-C groups in cyclopropane is equal to three. If H1, H2, and H3 are the group contributions, then we have

2H1 + H2 ) ∆f H 0(C2H6) ) -20.04 kcal/mol 8H1 + 2H2 + H3 ) ∆f H 0(C3H8) ) -25.02 kcal/mol It may be observed that in this case we have a linear system of two equations in three variables and, hence, the solution is not unique. This is not an issue since the strain energy is independent of the choice of the solution. For instance, we can assume that H1 ) 0 and solve the system for H2 and H3. This gives

H2 ) ∆f H 0(C2H6) ) -20.04 kcal/mol H3 ) ∆f H 0(C3H8) - 2∆f H 0(C2H6) ) 15.06.kcal/mol On the basis of these relations, we first estimate the enthalpy of formation of cyclopropane via the group additivity scheme

∆f H GA((CH2)3) ) 6H1 + 3H2 + 3H3 ) 3∆f H 0(C3H8) 3∆f H 0(C2H6) ) -14.94 kcal/mol and, finally, the strain energy

Comments

J. Phys. Chem. A, Vol. 114, No. 10, 2010 3733

∆H ) ∆f H GA(C3H6) - ∆f H 0(C3H6)

This gives the strain energy

) 3∆f H (C3H8) - 3∆f H (C3H6) 0

0

∆f H 0(C3H6) ) -27.68 kcal/mol It is seen that we obtained precisely the same stoichiometric expression, i.e., the enthalpy change of eq 1, and, hence, the same strain energy. That is, the Benson and Allen methods are equivalent. In a more direct way, the same result follows from the comparison of the echelon forms of the group matrices. Indeed, the group matrix for the Allen model may be readily brought to the following form

g)

[ ] 1 0 0 0 1 0 -3 3 0

Disregarding the last column, one sees that the group matrices of the Benson and Allen models are column equivalent and, consequently, Benson and Allen models possess the same stoichiometric expression represented by eq 1. It may be shown that precisely the same result is obtained by employing the classical Laidler6 model as well as more recent models proposed by Gronert3 and Rogers et al.7 A more complex example illustrating the equivalence of these group additivity models is presented in the Supporting Information. Protobranching is a Bond Additivity Model. We next prove that eq 2, which defines the protobranching strain energy of cyclopropane is the stoichiometric expression of the bond additivity model. For the list of species comprising methane, ethane, and cyclopropane there are two types of bonds, namely, g1 ) C-H and g2 ) C-C. Thus, the bond matrix is

∆H ) ∆f H GA(C3H6) - ∆f H 0(C3H6) ) -3∆f H 0(CH4) + 3∆f H 0(C2H6) ∆f H 0(C3H6) ) -19.19 kcal/mol

It follows that this expression coincides with the enthalpy change of eq 2 and, consequently, eq 2 is the stoichiometric expression of the bond additivity model. Because the bond additivity is inferior to the group additivity so is the strain energy evaluated via the bond additivity.

Multiple Reaction Schemes Group additivity models usually involve a large number of reference species. The stoichiometric expression of the group additivity methods in this case is given by a special type of reaction schemes referred to as group additivity response reactions (RERs). Here we illustrate the evaluation of the strain energy of cyclopropane employing the group additivity RERs approach.4 First, we apply it to conventional group additivity methods. Next, we use the same approach to show that protobranching is essentially a flawed group additivity method. For illustration purposes we use a simplified version of the group additivity methods comprising only seven reference species: ethane (C2H6), propane (C3H8), n-butane (C4H10), n-pentane (C5H12), n-hexane (C6H12), n-heptane (C7H14), and methane (CH4). Conventional Group Additivity Methods. For this subset of reference species the Benson model still requires only two groups, g1 ) CH3 and g2 ) CH2 so that the group additivity matrix is

The respective bond contributions H1 and H2 may be obtained solving the following system of linear equations

4H1 ) ∆f H 0(CH4) ) -17.89 kcal/mol 6H1 + H2 ) ∆f H 0(C2H6) ) -20.04 kcal/mol The solution is

H1 ) 1/4∆f H 0(CH4) ) -4.47 kcal/mol H2 ) ∆f H (C2H6) - 6/4∆f H (CH4) ) 6.795.kcal/mol 0

0

Hence, the enthalpy of formation of cyclopropane calculated via the bond additivity model is

∆f H GA(C3H6) ) 6H1 + 3H2 ) -3∆f H 0(CH4) + 3∆f H 0(C2H6) ) -6.45 kcal/mol

Here and below the arrow indicates elementary row operations to the transposed group additivity matrix aimed to bring it to an echelon form. It should be noted that methane is ruled out by the Benson model based on structural considerations; i.e., methane does not involve -CH3 and -CH2groups. According to the group additivity RERs approach, the performance of the group additivity may be qualitatively described by the enthalpy changes of the RERs involving the reference species. These can be generated from the group matrix as follows. Consider the matrix

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[ ]

J. Phys. Chem. A, Vol. 114, No. 10, 2010

1 0 -1 -2 -3 -4 -3

0 1 2 3 4 5 3

Comments

C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C3H6

the enthalpy changes of the RERs involving the reference species are equal to zero, the enthalpy changes of the RERs involving cyclopropane converge to the unique strain energy. For our system the subset of group additivity RERs involving cyclopropane along with their enthalpy changes is

According to the RERs formalism,4 every determinant of order three formed from this matrix is a RER. The total number of RERs is equal to the number of ways three species may be selected from a total of seven, i.e., 7!/3!/4! ) 35. In turn, these may be partitioned into two subsets of RERs. The first one, totaling 20 RERs, involves only the reference species. The enthalpy changes of these RERs qualitatively describe the performance of the group additivity method in that the closer to zero the enthalpy changes the better the performance of the group additivity model. The performance of a group additivity model also depends on a purely stoichiometric factor of the RERs.4 For our system the subset of RERs involving the reference species along with their enthalpy changes (kcal/mol) and stoichiometric factors γj is

F1: F2: F3: F4: F5: F6: F7: F8: F9: F10: F11: F12: F13: F14: F15: F16: F17: F18: F19: F20:

C2H6 + C4H10 ) 2C3H8 2C2H6 + C5H12 ) 3C3H8 3C2H6 + C6H14 ) 4C3H8 4C2H6 + C7H16 ) 5C3H8 C2H6 + 2C5H12 ) 3C4H10 C2H6 + C6H14 ) 2C4H10 3C2H6 + 2C7H16 ) 5C4H10 C2H6 + 3C6H14 ) 4C5H12 2C2H6 + 3C7H16 ) 5C6H12 C2H6 + 4C7H16 ) 5C6H14 C3H8 + C5H12 ) 2C4H10 2C3H8 + C6H14 ) 3C4H10 3C3H8 + C7H16 ) 4C4H10 C3H8 + 2C6H14 ) 3C5H12 C3H8 + C7H16 ) 2C5H12 C3H8 + 3C7H16 ) 4C6H14 C4H10 + C6H14 ) 2C5H12 2C4H10 + C7H16 ) 3C5H12 C4H10 + 2C7H16 ) 3C6H14 C5H12 + C7H16 ) 2C6H14

∆Hjo, kcal/mol 0.03 0.10 -0.02 -0.05 0.11 -0.08 -0.25 -0.46 -0.65 -0.10 0.04 -0.11 -0.17 -0.34 -0.25 -0.07 -0.19 -0.29 -0.01 0.09

γj2 1 1 1 1 1 4 1 1 1 1 1 1 1 1 4 1 1 1 1 1

It is seen that that the enthalpy changes of these RERs are indeed small and, hence, the group additivity model performs remarkably well. Now, consider the complete list of group additivity RERs involving cyclopropane. Because a RER in this system cannot involve more than 3 species and one of them should be cyclopropane, it follows that a RER cannot involve more than two reference species. That is, the number of group additivity RERs involving cyclopropane is equal to the number of ways two reference species may be selected from a total of six, i.e., 6!/2!/6! ) 15. Provided that the enthalpy changes of the RERs involving only reference species are small, the enthalpy changes of the RERs involving cyclopropane should be close to the strain energy. Ideally, when

F1: F2: F3: F4: F5: F6: F7: F8: F9: F10: F11: F12: F13: F14: F15:

C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6

+ + + + + + + + + + + + + + +

3C2H6 ) 3C3H8 3/2 C2H6 ) 3/2 C4H10 C2H6 ) C5H12 3/4 C2H6 ) 3/4 C6H14 3/5 C2H6 ) 3/5 C7H16 3C3H8 ) 3C4H10 3/2 C3H8 ) 3/2 C5H12 C3H8 ) C6H14 3/4 C3H8 ) 3/4 C7H16 3C4H10 ) 3C5H12 3/2 C4H10 ) 3/2 C6H14 C4H10 ) C7H16 3C5H12 ) 3C6H14 3/2 C5H12)3/2 C7H16 3C6H14 ) 3C7H16

∆Hjo, kcal/mol -27.68 -27.73 -27.78 -27.67 -27.65 -27.77 -27.83 -27.66 -27.64 -27.89 -27.61 -27.60 -27.32 -27.45 -27.59

The enthalpy changes of these reaction schemes expressing the strain energy of cyclopropane are remarkably close, thus reflecting the good performance of the group additivity model. As shown in the Supporting Information, the exact value of the strain energy of cyclopropane for this simple model is equal to 27.65 kcal/mol. Increasing the number of reference species and groups to 64 and 6, respectively, the final Benson model gives a strain energy of 27.74 kcal/mol. Most notably, the Benson model, as shown in the Supporting Information, is equivalent to other group additivity methods. Respectively, other group additivity models predict the same strain energy. Methane and Conventional Group Additivity Methods. As is well-known, methane is ruled out by any group additivity model for alkanes due to unique structural particularities. Here we prove that, alternatively, methane is ruled out as a reference species based on stoichiometric and linear algebra considerations. Formally, the proof requires a group additivity model that involves C-H bonds or groups, e.g., Allen or Gronert type of models. This is not a shortcoming since, as shown in the Supporting Information, all of the group additivity models for alkanes are equivalent. Adding methane to the list of reference species and employing the Allen model, for instance, one may generate the following group matrix

where g1 ) C-H, g2 ) C-C, and g3 ) C-C-C. From the structure of the group additivity matrix it is immediately seen

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that there is no way to construct group additivity RERs involving methane. Indeed, the group additivity RERs in this system are given by determinants of order four formed from the following matrix

[ ] 1 0 -1 -2 -3 -4 0 -3

0 1 2 3 4 5 0 3

0 0 0 0 0 0 1 0

C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 CH4 C3H6

It is seen that all RERs that do not involve methane are “zero” RERs due to a zero column in the determinant while in all RERs that involve methane the stoichiometric coefficients of methane are equal to zero. Thus, methane is ruled out by the conventional group additivity methods. Protobranching. Apparently, the evaluation of the strain energy according to the concept of protobranching has nothing to do with group additivity methods. This is not true. Here we show that protobranching is essentially a flawed group additivity method. Consider again the Allen model. Following the protobranching approach, we now assume that cyclopropane does not involve C-C-C groups. Thus, without methane the Allen group additivity matrix is

It may be seen that there is no way to generate group additivity RERs involving cyclopropane because the stoichiometric coefficient of cyclopropane in any group additivity RER is equal to zero. As a result, the evaluation of the strain energy of cyclopropane under the assumption that cyclopropane does not involve C-C-C groups completely fails. In other words, the assumption that there are no C-C-C groups in cyclopropane contradicts the conventional group additivity methods. Indeed, assuming that there are three C-C-C groups in cyclopropane the Allen model gives

That is, provided the number of C-C-C groups in cyclopropane is equal to three, the Allen model works and is identical to Benson’s model (and to all others). Adding methane as a reference species to the Allen model under the protobranching assumption, i.e., no C-C-C groups in cyclopropane, gives

Now, we face an interesting situation. The group additivity model is exactly the same as the conventional one; i.e., methane is ruled out as a reference species. The strain energy of cyclopropane, however, may still be evaluated. Indeed, the only way to obtain valid group additivity RERs involving cyclopropane, i.e., RERs with nonzero stoichiometric coefficient for cyclopropane is to require the presence of methane in any RER. Under this additional assumption, the stoichiometrically distinct group additivity RERs involving cyclopropane along with their enthalpy changes are

F1: F 2: F3: F4: F5: F6: F7: F8: F9: F10: F11:

C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6 C3H6

+ + + + + + + + + + +

3CH4 ) 3C2H6 3C4H10 + 3CH4 ) 6C3H8 3/2 C5H12 + 3CH4 ) 9/2 C3H8 C6H14 + 3CH4 ) 4C3H8 +3/4 C7H16 + 3CH4 ) 15/4 C3H8 6C5H12 + 3CH4 ) 9C4H10 3C6H14 + 3CH4 ) 6C4H10 2C7H16 + 3CH4 ) 5C4H10 9C6H14 + 3CH4 ) 12C5H12 9/2 C7H16 + 3CH4 ) 15/2 C5H12 12C7H16 + 3CH4 ) 15C6H14

∆Hoj , kcal/mol -19.19 -19.10 -19.04 -19.19 -19.22 -19.86 -19.37 -19.44 -20.39 -20.17 -19.79

These reactions perfectly balance the number of protobranches and, therefore, may be considered as the stoichiometric expression of the protobranching approach. The small differences in the enthalpy changes reflect the error of the group additivity model. Once the reference species are “equilibrated”, i.e., the experimental enthalpies of formation of the reference species are substituted with the calculated enthalpies of formation, the enthalpy change of any conceivable group additivity reaction converges to a unique value -19.28 kcal/mol representing the protobranching strain energy. A few examples illustrate this statement:

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J. Phys. Chem. A, Vol. 114, No. 10, 2010 C3H6 + 3CH4 ) 3C2H6

∆H01 ) 3∆f H calc(C2H6) - 3∆f H exp(CH4) - ∆f H exp(C3H6) ) 3(-20.07) - 3(-17.89) - 12.74 ) -19.28 kcal/mol F1: ∆H01

C3H6 + 3C4H10 ) 3CH4 + 6C3H8 ) 6∆f H calc(C3H8) - 3∆f H calc(C4H10) 3∆f H exp(CH4) - ∆f H exp(C3H6) ) 6(-25.04) - 3(-30.01) - 3(-17.89) - 12.74 ) -19.28 kcal/mol

From the above analysis it may be concluded that the protobranching approach is essentially a group additivity model. This confirms the general statement that there is no way to evaluate the strain energy other than employing a group additivity method. The protobranching group additivity model, however, is a very special one. First, eq 2 that defines the protobranching strain energy is just a special case of this group additivity model. Second, to evaluate the protobranching strain energy, it is not necessary to design a reaction scheme without protobranches, i.e., eq 2. Just the opposite, the same protobranching strain energy may be obtained by simply balancing the number of protobranches. Third, the overall statistical performance of the protobranching group additivity method is the same as the statistical performance of the conventional group additivity methods. Fourth, and most importantly, the concept of protobranching requires a mandatory presence of methane as a reference species. However, the role of methane is different from the role of a usual reference species. Namely, methane is a spectator reference species whose only purpose is to ensure the balance of C-H bonds. Discussion and Concluding Remarks The main message of this work is that there is no way to evaluate the strain energy other than via a group additivity method. We have clearly shown that the protobranching

Comments approach is not an exception. The main argument of protobranching that traditional group additivity methods do not balance the number of protobranches is unfounded because, if one really persists, the protobranches can be in principle balanced even if it is mistakenly assumed that there are no protobranches in cyclopropane. However, balancing protobranches comes at the price of forcing methane into a group additivity model for alkanes. This artificial procedure contradicts the very essence of group additivity approach. Conventional group additivity methods possess a low sensitivity with respect to the number of reference species. It means that removing one of the reference species has a small effect on the overall performance of the group additivity method. For the first time we face a group additivity model that is built around a single species, i.e., methane. Once methane is removed from the list of reference species, the entire group additivity model collapses. All of these inconsistencies are essentially due to the faulty assumption that the C-C-C groups and protobranches in strained hydrocarbons are different. The controversy may be naturally eliminated by recognizing that protobranches are equivalent to C-C-C groups. Supporting Information Available: Evaluation of the strain energy based on group additivity response reactions (RERs) formalism and equivalence of the conventional group additivity methods. This material is available free of charge via the Internet at http://pubs.acs.org. References and Notes (1) Wodrich, M. D.; Wannere, C. S.; Mo, Y.; Jarowski, P. D.; Houk, K. N.; Schleyer, P. v. R. Chem.sEur. J. 2007, 13, 7731–7744, DOI: 10.1002/chem.200700602. (2) Allen, T. L. J. Chem. Phys. 1958, 31, 1039–1049. (3) Gronert, S. J. Org. Chem. 2006, 71, 1209–1219. (4) Fishtik, I. J. Phys. Chem. A 2006, 110, 13264–13269. (5) Cohen, N.; Benson, S. W. Chem. ReV 1993, 93, 2419–2438. (6) Laidler, K. J. Can. J. Chem. 1956, 34, 626–648. (7) Zavitsas, A.; Matsunaga, N.; Rogers, D. W. J. Phys. Chem. A 2008, 112, 5734–5741.

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