Supplementary Material10.1007... · Web viewP9, d(C1 C5) = 1.687 Å and d(C3 C4) = 2.095 Å, the...

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Supplementary Material A Molecular Electron Density Theory study of [3+2] cycloaddition reactions of chiral azomethineylides with β-nitrostyrene Lilia Nasri a , Mar Ríos-Gutiérrez, b Abdelmalek Khorief Nacereddine a,c ,Abdelhafid Djerourou, a Luis R. Domingo b a Laboratoire de Synthèse et Biocatalyse Organique, Département de Chimie, Faculté des Sciences, Université Badji Mokhtar Annaba, BP 12, 23000 Annaba, Algeria. b Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, E-46100 Burjassot, Valencia, Spain. c Département de Physique et Chimie, Ecole Normale Supérieure d’Enseignement Technologique de Skikda, Azzaba, Skikda, Algeria Index S2 1. Analysis of the strong stabilities of MCb and TSmn-b S6 2. ELF topological analysis of the formation of the new C-C single bonds along the most favourable meta/endo/anti reaction channel of the 32CA reaction involving methyl- substituted AY 11b. S11 3. Theoretical background S12 3.1.Topological analysis of the electron localisation function (ELF) S13 3.2. Bonding Evolution Theory (BET) S14 3.4. Quantum Theory of Atoms in Molecules (QTAIM) S14 3.3. Non-Covalent interactions (NCIs) S15 4.References S17 Table S3. Gas phase MPWB1K/6-31G(d) and MPWB1K/6- 311G(d,p)//MPWB1K/6-31G(d) total and relative energies of the stationary points involved in the anti diastereoisomeric pathways associated with the 32CA reaction of AY 11b with NS 7. S18 Table S4. MPWB1K/6-31G(d) thermodynamic data computed at 110 ºC and 1 atm in toluene of the stationary points involved in the antidiastereoisomeric pathways associated with the 32CA reaction between AY 11b and NS 7.

Transcript of Supplementary Material10.1007... · Web viewP9, d(C1 C5) = 1.687 Å and d(C3 C4) = 2.095 Å, the...

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Supplementary Material

A Molecular Electron Density Theory study of [3+2] cycloaddition reactions of chiral azomethineylides with β-nitrostyrene

Lilia Nasria, Mar Ríos-Gutiérrez, bAbdelmalek Khorief Nacereddine a,c,Abdelhafid Djerourou,a

Luis R. Domingob

aLaboratoire de Synthèse et Biocatalyse Organique, Département de Chimie, Faculté des Sciences, Université Badji Mokhtar Annaba, BP 12, 23000 Annaba, Algeria.

bDepartment of Organic Chemistry, University of Valencia, Dr. Moliner 50, E-46100 Burjassot, Valencia, Spain.

cDépartement de Physique et Chimie, Ecole Normale Supérieure d’Enseignement Technologique de Skikda, Azzaba, Skikda, Algeria

Index

S2 1. Analysis of the strong stabilities of MCb and TSmn-bS6 2. ELF topological analysis of the formation of the new C-C single bonds along the

most favourable meta/endo/anti reaction channel of the 32CA reaction involving methyl-substituted AY 11b.

S11 3. Theoretical backgroundS12 3.1.Topological analysis of the electron localisation function (ELF)S13 3.2. Bonding Evolution Theory (BET)S14 3.4. Quantum Theory of Atoms in Molecules (QTAIM)S14 3.3. Non-Covalent interactions (NCIs)

S15 4.ReferencesS17 Table S3. Gas phase MPWB1K/6-31G(d) and MPWB1K/6-311G(d,p)//MPWB1K/6-

31G(d) total and relative energies of the stationary points involved in the anti diastereoisomeric pathways associated with the 32CA reaction of AY 11b with NS 7.

S18 Table S4. MPWB1K/6-31G(d) thermodynamic data computed at 110 ºC and 1 atm in toluene of the stationary points involved in the antidiastereoisomeric pathways associated with the 32CA reaction between AY 11b and NS 7.

S19 Table S5. MPWB1K/6-31G(d) total and relative energies of the stationary points involved in the meta/anti pathways of the 32CA reaction of AY 11a with NS 7.

S20 Table S6. MPWB1K/6-31G(d) thermodynamic data computed at computed at 110 ºC and 1 atm in toluene of the stationary points involved in the meta/anti pathways of the 32CA reaction between AY 11a and NS 7.

S21 Table S7. Valence basin populations calculated from the ELF of the intrinsic reaction coordinate (IRC) points, P1 – P10, defining the eleven phases characterising the molecular mechanism of the polar pdr-type 32CA reaction between AY 11b and NS7.

S22 MPWB1K/6-31G(d) computed total energies and Cartesian coordinates in gas phase of the structures involved in the anti diastereoisomeric pathways associated with the 32CA reaction of AY 11b with NS 7, and in the meta/anti pathways of the 32CA reaction of AY 11a with NS 7.

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1. Analysis of the strong stabilities of MCb and TSmn-b.

The very low relative energies of MCband TSmn-b suggest that some type of

electrostatic or non-covalent interactions may be strongly stabilising both structures. The

analysis of the geometries of MCb and TSmn-b shows that one oxygen atom of the nitro

group of NS 7 is oriented towards the AY H6 hydrogen atom, due to the acidic character of

the latter. The O···H6 distances are 2.37 at MCb and 2.25Å and TSmn-b, respectively. These

short distances suggest the formation of an HB between these atoms, which might justify the

strong stabilisation of MCb and TSmn-b.

In order to confirm the presence of an O···H6 HB in these species, a topological

analysis of the favourable Non-Covalent Interactions (NCIs)[1] taking place at MCb and

TSmn-b was performed. Bonding NCI gradient isosurfaces are shown in Figure S1, while

thereduced density gradients are represented in Figure S2. The topological analysis of the

favourable NCIs at MCb and TSmn-b shows the presence of several small and green surfaces

between the two AY and NS frameworks, associated with weak, favourable non-covalent

interactions such as Van der Waals interactions or HBs. Particularly noteworthy is the small

circular surface observed between one of the oxygen atoms of the nitro group of the NS

fragment and the acidic H6 hydrogen of the AY moiety, confirming the existence of a weak

O···H6 HB at both MCb and TSmn-b.

In order to verify the low strengh of these HBs, a Quantum Theory of Atoms in

Molecules (QTAIM)[2]topological analysis of the electron density in the O···H6 region at

MCb and TSmn-b was carried out. The QTAIM parameters of the critical points (cps) found

in the O···H6 regions are presented in Table S1, while the representation of the contour line

maps of the Laplacian of the electron density on the molecular plane defined by the O···H6C

atoms is shown in Figure S3.

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Figure S1. Favourable NCI gradient isosurfacesof MCb and TSmn-b, represented at an isovalue of 0.5 a.u., together with the representation of the contour line maps of the Laplacian of the electron density of both structures on the molecular plane defined by the O···H6C atoms. Bonding critical points (bcps) with bcp< 0 are coloured in blue, while bcps with bcp> 0 are coloured in red.

Figure S2.Plots of the reduced density gradient (RDG) versus the electron density multiplied by the sign of the second Hessian eigenvalue for MCb and TSmn-b. Both quantities are given in a.u.

Numerous studies encountered that the strength of interaction, particularly of HBs, is

expressed by the characteristics of the H···X bonding critical point (bcp).[3] The increase of

the strength of HBs is associated with the increase of the electron density at the H···X bcp,

bcp, with the increase of the kinetic energy electron density, Gbcp, the decrease of the potential

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energy (the increase of its modulus), Vbcp,and the decrease of the total electron energy density,

Hbcp, at the bcp.[4] The relation between the strength of interaction, and particularly, the

H···X distance, and the Laplacian,bcp, is more complicated; starting from the weakest

HB, the positive value of the Laplacian increases with the augmentation of the strength of

interaction. However, for very strong hydrogen bonds, it decreases and is even negative.[5]

Table S1shows that the electron density associated to bcp(1) at MCb, bcp(1) = 0.013 a.u.

and bcp(1) = 0.048 a.u., and that associated to bcp(2) at TSmn-b, bcp(2) = 0.016 and bcp(2)

= 0.060, presents similar values. The low values of bcp< 0.06 and the positive sign of

Laplacian 2bcp> 0 indicate that these (3,-1) bcps are associated with weak O···H6 HBs, in

agreement with the NCI topological analysis. Note that for some of the weakest HBs bcp

values ≤ 0.03 a.u. and Hbcp values very close to 0 were found,[6] such as those reported for

MCb and TSmn-b.

Table S1. QTAIM parameters, in a.u., of the (3,-1) bcps present in the O···H6 regions in MCb and TSmn-b, namely, the electron density bcp, its Laplacian bcp and the total electron energy density Hbcp.

bcp bonding region cbcp bcp Hbcp

MCb (1) O···H6 0.013 0.048 0.00

1

TSmn-b (2) O···H6 0.01

6 0.060 0.001

Given the weakness of the O···H6 HBs, feasible electrostatic interactions, such as

dipole-dipole interactions and local electrostatic interactions, were further analysed in order to

explain the strong stabilities of MCb and TSmn-b. On the one hand, the total dipole moments

are 5.09 D at AY11b, 5.77 D at NS 7, 3.85 D atMCb and 5.21 D at TSmn-b. As the total

dipole moment of MCb is smaller than that of any of the two separated reagents, it can be

concludedthat some dipolar interactions stabilising MCb are also feasible. On the other hand,

the MEP of MCb given in Figure 5 of the manuscriptshows a favourable electrostatic

interaction between the nitro group of NS 7, negatively charged, and the C3H and H6

hydrogen atoms of AY 11b, positively charged. The fact that these interactions are also

present at TSmn-a andTSmx-a (seeSection 3.3.3 of the manuscript) suggests that they are

also maintained along the reaction towards the corresponding TSmn-b.

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In summary, the strong stabilisation of both MCb and TSmn-b arises from a series of

favourable non-covalent (HBs) and electrostatic (dipolar and potential) interactions,

confirming that they are responsible for the feasibility of the polar pdr-type 32CA reactions

between AYs 11a,b and NS 7, rather than the polar character of the reaction.

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2. Electron Localisation function (ELF)topological analysis of the formation of the new C-C single bonds along the most favourable meta/endo/anti reaction channel of the 32CA reaction involving methyl-substituted AY 11b.

In order to confirm the pdr-type reactivity of AYs 11a,b and to understand the CC

single bond formation processes along the polar 32CA reactions of AYs 11a,b with NS 7, an

ELF [7] topological analysis of the stationary points as well as of the most relevant points

implied in the formation of the new CC single bonds along the IRC associated with the most

favourable meta/endo/anti reaction channel of the 32CA reaction involving methyl-substituted

AY 11b, is carried out. A BET procedure was used for the selection of the mentioned points

(those defining the phases in which the bond formation takes place and those defining the

previous ones). The populations, among other relevant parameters, of the most significant

valence basins (those associated with the bonding regions directly involved in the reaction) of

the selected points of the IRC, Pi, defining the different topological phases are included in

Table S7, while those of the stationary points and the points involved in the formation of the

new CC single bonds are displayed in Table S2. Additionally, the ELF attractor positions as

well as ELF localisation domains of the TS and the points involved in formation of the new

CC single bonds are shown in Figures S3and Figure 6of the manuscript, respectively.

At MCb, d(C1C5) = 2.929 Å and d(C3C4) = 3.091 Å, the ELF topological

characteristics of the separated reagents, AY 11b and NS 7, are maintained (see Section 3.1 of

the manuscript and Table S2). The three V(C1), V(C3) and V’(C3) monosynaptic basins

present at AY 11b, which are related to the two C1 and C3 pseudoradicalcenters that allow

establishing its pseudodiradical structure,[8] are also observed at the AY framework of MCb

integrating 0.63e, 0.31e and 0.23e, respectively. The two V(C1,N2) and V(N2,C3) disynaptic

basins associated with the two C1N2 and N2C3 bonding regions have populations of 2.45e

and 3.00e, while the two V(C4,C5) and V’(C4,C5) disynaptic basins present in the NS moiety

with a total electron population of 3.52e are related to the C4C5 double bond of NS 7. At

MCb, stabilised by 12.0 kcal·mol-1 with respect to the separated reagents, the GEDT is

negligible, 0.04e.

At TSmn-b, d(C1C5) = 2.216 Å and d(C3C4) = 2.524 Å, one of the two

monosynaptic basins associated with the C3 pseudoradicalcenter, the V’(C3) one, which is

situated on the syn face of the AY fragment, has disappeared. This topological change is the

consequence of the loss of the planar C3 environment, which is a change demanded for the

CC bond formation. Note, however, that the corresponding total population has also

decreased by ca. a half to 0.30e. This lost electron density has been redistributed into the

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adjacent V(N2,C3) disynaptic basin, whose population has increased to 3.50e. Otherwise,

together with the decrease of the population of the V(C1,N2) disynaptic basin to 2.28e, the

V(C1) monosynaptic basin has doubled its population to 0.62e. However, it should be

emphasised that coming from MCb to TSmn-b, this monosynaptic basin disappeared at

d(C1C5) = 2.673 Å as a consequence of the delocalisaton of its associated electron density

into the adjacent bonding region of the imidazolidine ring, and then again appeared at

d(C1C5) = 2.562 Å. In addition, at TSmn-b, the two V(C4,C5) and V’(C4,C5) disynaptic

basins present at the NS moiety have merged into a new V(C4,C5) disynaptic basin

integrating only 0.02e less than at MCb. The GEDT at TSmn-b, situated 6.3 kcal·mol-1

below the separated reagents, is 0.27e (see Section 3.3.1 of the manuscript), a high value that

allows establishing the strong polar character of this pdr-type 32CA reaction.

The changes in electron density taking place coming from MCb to TSmn-b, which can

be mainly associated to the depopulation of the C3 pseudoradicalcenter as well as the loss of

the planar sp2 hybridisation of the C3 carbon required for the CC single bond formation,

demand an energy cost of 5.7 kcal·mol-1.

At P7, d(C1C5) = 2.141 Å and d(C3C4) = 2.487 Å, two new V(C4) and V(C5)

monosynaptic basins, integrating 0.38e and 0.20e, are observed at the NS framework. The

electron density of these monosynaptic basins, which correspond to two C4 and C5

pseudoradicalcenters, mainly proceeds from the depopulation of the V(C4,C5) disynaptic

basin to 2.96e. The other two V(C1) and V(C3) monosynaptic basins have maintained their

populations. Note that the four V(C1), V(C2), V(C3) and V(C4) monosynaptic basins

demanded for the formation of the new V(C,C) disynaptic basins are simultaneously present

at this point (see P7 in Figure S3). Another noticeable topological change at P7 is the

presence of a new V(N2) monosynaptic basin, integrating 0.69e, while the population of the

V(N2,C3) disynaptic basin has decreased to 2.79e. This V(N2) monosynaptic basin is

associated with an N2 pseudoradical center that will further become a non-bonding N2

nitrogen lone pair at the final pyrrolo imidazole12n-b. At P7, situated 6.6 kcal·mol-1 below

the separated reagents, prior to the formation of the new CC single bonds, the GEDT has

slightly increased to 0.30e.

At P8, d(C1C5) = 2.019 Å and d(C3C4) = 2.414 Å, the first most relevant topological

change along the reaction path takes place; the two V(C1) and V(C5) monosynaptic basins

present at the previous point P7 have merged into a new V(C1,C5) disynaptic basin

integrating an initial population of 1.19e (see P8 in Figure S3). This relevant topological

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change indicates that the formation of the new C1C5 single bond begins at a C1C5 distance

of ca. 2.02 Å through the C-to-C coupling of two C1 and C5 pseudoradicalcenters. Note that

the C1 and C5 carbons correspond to the most nucleophilic and electrophilic centers of AY

11b and NS 7, respectively.At the same time, together with the depopulation of the V(C4,C5)

disynaptic basin to 2.69e, the population of the V(C4) monosynaptic basin of the NS fragment

has increased to 0.52e, while that of the V(C3) monosynaptic basin still remains invariable.

Note that the population of this V(C3) monosynaptic basin has remained practically

unchanged along the reaction path (see Table S7). At P8, situated 8.5 kcal·mol-1 below the

separated reagents, together with the formation of the first C1C5 single bond, the GEDT

reaches the maximum value along the reaction path, 0.34e.

At P9, d(C1C5) = 1.687 Å and d(C3C4) = 2.095 Å, the second most relevant

topological change along the reaction path takes place; likewise to what happens at P8, the

two V(C3) and V(C4) monosynaptic basins previously present have merged into a new

V(C3,C4) disynaptic basin integrating an initial population of 1.36e (see P9 in Figure S3).

This significant topological change indicates that the formation of the second C3C4 single

bond begins at a C3C4 distance of ca. 2.10 Å through the C-to-C coupling of two C3 and C4

pseudoradical centers. At P9, situated 27.1 kcal·mol-1 below the separated reagents, the

GEDT has decreased to 0.28e as the consequence of a retro-donation process from the NS

towards the AY moieties.

Finally, at 12n-b, d(C1C5) = 1.549 Å and d(C3C4) = 1.546 Å, the two V(C1,C5) and

V(C3,C4) disynaptic basins have reached populations of 1.87e and 1.88e, and the V(C1,N2),

V(N2,N3) and V(C4,C5) disynaptic basins integrate 1.68e, 1.77e and 1.97e. The presence of

two V(N2) and V’(N2) monosynaptic basins characterising the non-bonding N2 nitrogen lone

pair, with electron populations of 2.14e and 0.28e, which is indicative of a more or less planar

arrangement, is noteworthy. The great difference between the populations of both V(N2) and

V’(N2) monosynaptic basins accounts for an inexact planar configuration. At 12n-b, situated

61.8 kcal·mol-1 below the separated reagents, the GEDT is again very low, 0.07e.

Table S2. Valence basin populations calculated from the electron localisation function (ELF) of the stationary points MCb, TSmn-b and 12n-b, and the IRC points P7 – P9defining Phases VIII – X involved in the formation of the new C1C5 and C3C4 single bonds along the polar pdr-type 32CA reaction between AY 11b and NS 7. Distances are given in angstroms, Å, GEDT values and electron populations in average number of electrons, e, and relativea energies in kcal·mol-1.

  11b 7 MCb TSmn-b P7 P8 P9 12n-b

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d(C1C5) 2.929 2.216 2.141 2.019 1.687 1.549d(C3C4) 3.091 2.524 2.487 2.414 2.095 1.546E -12.0 -6.3 -6.6 -8.5 -27.1 -61.8GEDT 0.04 0.27 0.30 0.34 0.28 0.07V(C1,N2) 2.46 2.45 2.28 2.17 2.02 1.75 1.68V(N2) 0.69 1.01 1.72 2.14V’(N2) 0.28V(N2,C3) 2.97 3.00 3.32 2.79 2.65 2.31 1.77V(C4,C5) 1.78 1.73 3.50 2.96 2.69 2.15 1.97V’(C4,C5) 1.78 1.78V(C1) 0.59 0.63 0.62 0.68V(C3) 0.32 0.31 0.30 0.30 0.30V’(C3) 0.29 0.23V(C4) 0.38 0.52V(C5) 0.20V(C1,C5) 1.19 1.68 1.87V(C3,C4) 1.36 1.88

a Relative to the separated reagents AY 11b and NS 7.

Figure S2. ELF attractor positions of TSmn-b and the points of the IRC defining Phases VII – IX involved in the formation of the new C1C5 and C3C4 single bonds along the polar pdr-

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type 32CA reaction between AY 11b and NS7. The electron populations, in e, are given in brackets.

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3. Theoretical background

Like many other chemical concepts, chemical bonds are defined in a rather ambiguous

manner as they are not observable, but rather belong to a representation of the matter at a

microscopic level, which is not fully consistent with quantum mechanical principles. To

harmonise the chemical description of matter with quantum chemical postulates, several

mathematical models have been developed. Among them, the theory of dynamical systems

[9], convincingly introduced by Bader through the QTAIM [2], has become a powerful

method of analysis. The QTAIM enables a partition of the electron density within the

molecular space into basins associated with atoms. Another appealing procedure that provides

a more straightforward connection between the electron density distribution and the chemical

structure is the quantum chemical analysis of the ELF of Becke and Edgecombe. [7] ELF

constitutes a useful relative measure of the electron pair localisation characterising the

corresponding electron density [10,11]. Finally, NCIs[1] have a unique fingerprint and their

presence can be revealed solely by means of electron density analysis. They are highly non-

local and manifest in real space as low-gradient isosurfaces with low densities.

3.1. ELF

Within the framework of Density Functional Theory (DFT)[12], ELF is a density-based

property that can be interpreted in terms of the positive-definite local Pauli and Thomas Fermi

kinetic energy densities in a given system. In the validity of such a framework, these

quantities provide key information to evaluate the relative local excess of kinetic energy

density associated to the Pauli principle. ELF presents values in the range [0,1][13]; the

highest values being associated with the spatial positions with higher relative electron

localisation [14-17]. After an analysis of the electron density, ELF provides basins of

attractors, which are the domains in which the probability of finding an electron pair is

maximal. The spatial points in which the gradient of ELF has a maximum value are

designated as attractors [18]. ELF basins are classified as core basins, C(...), and valence

basins, V(...). The latter are characterised by the synaptic order, i.e. the number of atomic

valence shells in which they participate. Thus, there are monosynaptic, disynaptic, trisynaptic

basins and so on [16]. Monosynaptic basins, labelled V(A), correspond to the lone pairs or

non-bonding regions, while disynaptic basins, labelled V(A,B), connect the core of two nuclei

A and B and, thus, correspond to a bonding region between A and B. This description

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recovers the Lewis bonding model, providing a very suggestive graphical representation of

the molecular system.

3.2. BET

When trying to achieve a better understanding of bonding changes in organic chemical

reactions, the so-called Bonding Evolution Theory (BET) has proved to be a very useful

methodological tool [19]. BET applies Thom’s Catastrophe Theory (CT) concepts [20-22] to

the topological analysis of the gradient field of the ELF.

Within the BET methodology [19], the structural stability of the critical points of the

ELF gradient field is examined for the system of nuclei and electrons ‘evolving’ along the

Born-Oppenheimer energy hypersurface or a given reduced reaction coordinate, e.g. the

intrinsic reaction coordinate, occurring as a result of the variation in the control space

parameters from reactive to product configurations. The chemical process becomes thus

rationalised in terms of successive structural stability domains (SSDs), also called phases,

comprising structures along the path where the number and type, e.g. synaptic orders, of

critical points of the gradient field of ELF remain without changes [19].

Within the BET context, the turning points between these phases are located and the

discontinuities or bifurcation catastrophes can be identified. BET allows, thus, characterising

unequivocally the behaviour of the dynamical system upon bifurcations associated with the

ELF gradient field changing along the reaction coordinate. The different catastrophes in this

case correspond to the reduction or the increase of the critical points associated with attractors

of electron pairs defining bonding and non-bonding, e.g. lone pairs, domains for electron

(de)localisation.

A detailed examination of the topology of ELF along the IRC pathway for a given

reaction reveals the existence of several catastrophes belonging exclusively to the fold, F and

F†, and cusp, C and C†, elementary types, according to Thom’s classification. The F

catastrophe merges an attractor and a saddle point into a wandering point, i.e. a non-critical

point, decreasing the number of basins by 1, whereas F† splits a wandering point into an

attractor and a saddle point increasing the number of basins by 1. The † superscript is used in

those catastrophes in which either the number of attractors or the synaptic order increase. The

cusp catastrophe C merges two attractors and a saddle point into an attractor decreasing the

number of basins by 1, while C† splits an attractor into two attractors and a saddle point

increasing the number of basins by 1. The symbol of a catastrophe written in bold is used to

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mark a catastrophe leading to the formation of the first covalent bond. The analysis of the

changes in the number and type of ELF valence basins for the structures involved along the

IRC of the reaction allows establishing a set of points, Pi, separating the different phases that

characterise the studied molecular mechanism.

Several theoretical studies have shown that the topological analysis of the ELF offers a

suitable framework for the study of the changes of electron density.[23-29] This

methodological approach is used as a valuable tool to understand the bonding changes along

the reaction path and, consequently, to establish the nature of the electronic rearrangement

associated with a given molecular mechanism within the BET perspective.

3.3. QTAIM

QTAIM analysis of the electron density provides a series of critical points (cps),

which are points of the molecular space where (r) = 0.[2] The presence of a (3,-1) cp

appears to provide the boundaries between the basins of neighbouring atoms, being called a

bonding cp (bcp). Thus, the existence of a (3,-1) bcp and its associated atomic interaction line

indicates that electron density is accumulated between the nuclei linked in such a manner. The

Laplacian of the electron density in a cp, bcp, is a very appealing property that determines

where bcp is locally concentrated, bcp< 0, and locally depleted,bcp> 0. Thus, the sign of

bcp determines which of these two competing effects is dominant, allowing the

characterisation of (3,-1) bcps associated with covalent bonds, bcp< 0 and high bcp values,

and those associated with ionic bonds or weak non-covalent interactions such as hydrogen

bonds or van der Waals interactions, bcp> 0 and low bcp values.

3.4. NCIs

The sign of the Laplacian of the density, , is a widely used tool to distinguish

between different types of strong interactions.[1] To analyse bonding in more detail, the

Laplacian is often decomposed into a sum of contributions. These components are the three

eigenvalues λi of the electron density Hessian matrix, such that = λ1 + λ2 + λ3. Analysis of

these components has been widely applied to chemical bonding. The sign of λ2can be used to

distinguish bonding (λ2< 0) from non-bonding (λ2> 0) interactions.

The gradient isosurfaces provide a useful visualisation of NCIs as broad regions of real

space, rather than simple pairwise contacts between atoms, and are coloured according to the

corresponding values of sign(λ2). Analysis of the sign of λ2 thus helps to differentiate

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between different types of NCIs, whereas the density itself provides information about their

strength. Surfaces with very low density values (< |0.005| a.u.) generally represent weaker

dispersion interactions, while surfaces with slightly higher density values (|0.005| << |0.05|

a.u.) represent stronger NCIs, including both attractive HBs and steric clashes. On the other

hand, large negative values of sign(λ2) are indicative of strong attractive interactions and are

coloured in blue, while if the sign(λ2) is large and positive, the interactions are non-bonding

and are coloured in red; values near zero indicate weak Van der Waals interactions, and are

coloured in green.

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4. References

1. Johnson. E. R, Keinan. S, Mori-Sanchez. P, Contreras-García. J, Cohen. J. and Yang. A. W. J. Am. Chem. Soc., 2010,132, 6498.

2. Bader, R. F. W. Atoms in Molecules. A Quantum Theory; Claredon Press, Oxford, U.K, 1990.

3. (a) Rozas. I, Alkorta. I, Elguero. J. J. Am. Chem. Soc. 2000, 122, 11154; (b) Grabowski S. J, Sokalski. W. A, Dyguda. E, Leszczynski. J, J. Phys. Chem. B 2006, 110, 6444.

4. Grabowski. S. J. Chem. Rev. 2011, 111, 2597.

5. Espinosa. E, Alkorta. I, Elguero. J, Molins. E. J. Chem. Phys. 2002, 117, 5529.

6. Fuster. F, S. Grabowski. J. J. Phys. Chem. A 2011, 115, 10078.

7. Beck. A. D, Edgecombe. K. E. J. Chem. Phys.1990, 92, 5397.

8. Domingo. L. R, Chamorro, E. Pérez. P. Lett. Org. Chem.2010, 7, 432.

9. Abraham. R. H, Shaw. C. D. Dynamics: The Geometry of Behavior, Addison-Wesley, Redwood City, CA, 1992.

10. Silvi. B, Savin. A. Nature 1994, 371, 683.

11. Savin. A, Silvi. B, Colonna. F. Can. J. Chem.1996, 74, 1088.

12. Hohenberg. P, Kohn. W. Inhomogeneous electron gas Kohn. W. Physical Review 1964, 136, B864

13. Savin. A, Becke. A. D, Flad. J, Nesper. R, Preuss. H, Vonschnering. H. G. A. Angew. Chem. Int. Ed.1991, 30, 409.

14. Savin. A, Nesper. R, Wengert. S, Fassler. T. F. Angew. Chem. Int. Ed.1997, 36, 1809.

15. Savin. A. J. Chem. Sci. 2005, 117, 473.

16. Silvi. B. J. Mol. Struct. 2002, 614, 3.

17. Krokidis. X, Noury. S, Silvi. B. J. Phys. Chem. A 1997, 101, 7277.

18. Savin. A. J. Chem. Sci. 2005, 117, 473.

19. Krokidis. X, Noury. S, Silvi. B. J. Phys. Chem. A 1997, 101, 7277

20. Thom, R. Structural Stability and Morphogenesis: An Outline of a General Theory of

Models, Inc., Reading, Mass (London-Amsterdam, 1976).

21. Woodcock. A. E. R, Poston. T. A Geometrical Study of Elementary Catastrophes,

(Spinger-Verlag, Berlin, 1974).

22. Gilmore. R. Catastrophe Theory for Scientists and Engineers (Dover, New York, 1981).

23. Berski. S, Andrés. J, Silvi. B, Domingo. L.R. J. Phys. Chem. A 2003, 107, 6014–6024.

24. Chamorro. E. J. Chem. Phys. 2003, 118, 8687.

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25. Polo. V, Andrés. J, Berskit. S, Domingo. L. R, Silvi. B. J. Phys. Chem. A 2008, 112,

7128.

26. Domingo. L. R, Chamorro. E, Pérez. P. J. Org. Chem.2008, 73, 4615.

27. Domingo. L. R, Chamorro. E, Pérez. P. Org. Biomol. Chem.2010, 8, 5495.

28. Berski. S, Ciunik. Z. Mol. Phys. 2015, 113, 765.

29. Ríos-Gutiérrez. M, Pérez. P, Domingo. L. R. RSC Adv. 2015, 5, 58464.

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Table S3.Gas phaseMPWB1K/6-31G(d) and MPWB1K/6-311G(d,p)//MPWB1K/6-31G(d) total (E, in au) and relativea (E, in kcal·mol-1) energies of the stationary points involved in the anti diastereoisomeric pathways associated with the 32CA reaction of AY 11b with NS 7.

MPWB1K/6-31G(d) MPWB1K/6-311G(d,p)// MPWB1K/6-31G(d)

Structure E E E E11b -650.071519 -650.2218097 -513.897911 -514.019369MCb -1163.988607 -12.0 -1164.261069 -12.5TSmn-b -1163.979447 -6.3 -1164.251052 -6.2TSmx-b -1163.975194 -3.6 -1164.246880 -3.6TSon-b -1163.972694 -2.0 -1164.244845 -2.3TSox-b -1163.966730 1.7 -1164.238095 1.912n-b -1164.067847 -61.8 -1164.336665 -59.912x-b -1164.061845 -58.0 -1164.330470 -56.013n-b -1164.066105 -60.7 -1164.334521 -58.613x-b -1164.065427 -60.2 -1164.334521 -58.6

a Relative to the separated reagents AY 11b and NS 7.

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Table S4. MPWB1K/6-31G(d) enthalpies (H, in a.u), entropies (S, cal·mol−1·K−1) and Gibbs free energies (G, in a.u.), and relativea enthalpies (H, in kcal·mol−1), entropies (S, cal·mol−1·K−1) and Gibbs free energies (G, in kcal·mol−1), computed at 110 ºC and 1 atm in toluene, of the stationary points involved in the antidiastereoisomeric pathways associated with the 32CA reaction between AY 11b and NS 7.

Structure H H S S G G11b -649.806754 131.3 -649.8869107 -513.745913 106.1 -513.810683MCb -1163.563529 -6.8 185.7 -51.6 -1163.676944 13.0TSmn-b -1163.559573 -4.3 180.2 -57.1 -1163.669612 17.6TSmx-b -1163.555118 -1.5 180.4 -56.9 -1163.665277 20.3TSon-b -1163.552274 0.2 177.2 -60.1 -1163.660476 23.3TSox-b -1163.547359 3.3 186.1 -51.3 -1163.660990 23.012n-b -1163.640463 -55.1 183.0 -54.4 -1163.752177 -34.312x-b -1163.634987 -51.7 179.7 -57.6 -1163.744722 -29.613n-b -1163.639012 -54.2 178.8 -58.6 -1163.748163 -31.713x-b -1163.638688 -54.0 178.8 -58.5 -1163.747882 -31.6

a Relative to the separated reagents AY 11b and NS 7.

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Table S5. MPWB1K/6-31G(d) total (E, in au) and relativea (E, in kcal·mol-1) energies of the stationary points involved in the meta/anti pathways of the 32CA reaction of AY 11a with NS 7.

Structure E E11a -767.9396777 -513.897911MCa -1281.858351 -13.0TSmn-a -1281.849493 -7.5TSmx-a -1281.843411 -3.712n-a -1281.938846 -63.512x-a -1281.929820 -57.9

a Relative to the separated reagents AY 11b and NS 7.

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Table S6. MPWB1K/6-31G(d) enthalpies (H, in a.u), entropies (S, cal·mol−1·K−1) and Gibbs free energies (G, in a.u.), and relativea enthalpies (H, in kcal·mol−1), entropies (S, cal·mol−1·K−1) and Gibbs free energies (G, in kcal·mol−1), computed at 110 ºC and 1 atm in toluene, of the stationary points involved in the meta/anti pathways of the 32CA reaction between AY 11a and NS7.

Structure H H S S G G11a -767.581023 149.9 -767.6725277 -513.745913 106.1 -513.810683MCa -1281.341005 -8.8 204.7 -51.2 -1281.465991 10.8TSmn-a -1281.334391 -4.7 201.9 -54.0 -1281.457679 16.0TSmx-a -1281.329324 -1.5 198.1 -57.8 -1281.450292 20.712n-a -1281.418162 -57.2 200.6 -55.4 -1281.540638 -36.012x-a -1281.410617 -52.5 201.9 -54.1 -1281.533880 -31.8a Relative to the separated reagents AY 11b and NS 7.

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Table S7. Valence basin populations calculated from the electron localisation function (ELF) of the intrinsic reaction coordinate (IRC) points, P1 – P10, defining the eleven phases characterising the molecular mechanism of the polar pdr-type 32CA reaction between AY 11b and NS7. The stationary points MCb, TSmn-b and 12n-b are also included. Distances are given in Å, GEDT values and electron populations in average number of electrons, e, and relativea energies in kcal·mol-1.

  11b 7 MCb P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 12n-b TSmn-b

Catastrophes F F† F C F† F† F† C C F†

Phases I II III IV V VI VII VIII IX X XId(C1C5) 2.929 2.673 2.562 2.501 2.424 2.202 2.147 2.141 2.019 1.687 1.681 1.549 2.216d(C3C4) 3.091 2.875 2.771 2.722 2.666 2.520 2.490 2.487 2.414 2.095 2.083 1.546 2.524E -12.0 -9.9 -8.9 -8.3 -7.5 -6.3 -6.5 -6.6 -8.5 -27.1 -27.7 -61.8 -6.3GEDT 0.04 0.10 0.14 0.16 0.19 0.28 0.30 0.30 0.34 0.28 0.28 0.07 0.27V(C1,N2) 2.46 2.45 2.51 2.50 2.48 2.46 2.26 2.18 2.17 2.02 1.75 1.76 1.68 2.28V(N2) 0.57 0.67 0.69 1.01 1.72 1.73 2.14V’(N2) 0.06 0.28V(N2,C3) 2.97 3.00 2.98 3.05 3.11 3.11 2.80 2.80 2.79 2.65 2.31 2.22 1.77 3.32V(C4,C5) 1.78 1.73 1.83 1.87 1.87 3.47 3.52 3.32 2.96 2.69 2.15 2.14 1.97 3.50V’(C4,C5) 1.78 1.78 1.66 1.65 1.62V(C1) 0.59 0.63 0.30 0.32 0.40 0.62 0.67 0.68 0.62V(C3) 0.32 0.31 0.32 0.32 0.33 0.32 0.30 0.30 0.30 0.30 0.30V’(C3) 0.29 0.23 0.17 0.13V(C4) 0.38 0.52V(C5) 0.20 0.20V(C1,C5) 1.19 1.68 1.69 1.87V(C3,C4) 1.36 1.36 1.88

a Relative to the separated reagents AY 11b and NS7.

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MPWB1K/6-31G(d) computed electronic energies and Cartesian coordinates in gas phase of the structures involved in the anti diastereoisomeric pathways associated with the 32CA reaction of AY 11b with NS 7, and in the meta/anti pathways of the 32CA reaction of AY 11a with NS 7.

7

E(RmPW+HF-B95) = -513.897911283 a.u.

C -0.61503000 -0.43390700 -0.00001000C -1.59309800 0.46246000 0.00000000H -0.91993600 -1.47132100 -0.00002300H -1.51046700 1.53336000 0.00001300C 0.81129100 -0.16606700 -0.00000500C 1.68124900 -1.25225100 0.00000500C 1.34664900 1.12146600 -0.00000900C 3.04928200 -1.06371800 0.00000800H 1.27453900 -2.25295100 0.00001000C 2.71167400 1.30969200 -0.00000300H 0.69048000 1.97851800 -0.00001600C 3.56694400 0.21825300 0.00000500H 3.71042900 -1.91638700 0.00001500H 3.11359400 2.31115700 -0.00000700H 4.63530200 0.37118200 0.00001000N -2.96276900 0.03010700 -0.00000900O -3.79213000 0.91268800 0.00001900O -3.20891000 -1.15517300 -0.00000400

11b

E(RmPW+HF-B95) = -650.071518813 a.u.

C -1.83804400 -1.05521300 -0.10833400C -0.91919900 1.04895700 -0.07093900H -1.80404100 -1.74995900 -0.94873200H -0.19982500 1.83518400 -0.15067700C -2.34132200 1.20496900 -0.17122200O -3.01207500 2.21324300 -0.18746600N -0.59273700 -0.24715900 -0.14586200C 0.55166800 -0.89529600 -0.21931500H 0.45525700 -1.95257200 -0.40421300N -2.85081200 -0.07483100 -0.27694400C -4.24808000 -0.35648900 -0.28638200H -4.59432200 -0.80381100 0.64687900H -4.74867000 0.59737700 -0.41876800H -4.51439900 -1.01699000 -1.11130600C -1.92898800 -1.80504000 1.20227300H -2.85448900 -2.37409600 1.24013700

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H -1.09702700 -2.49501600 1.31329400H -1.91664200 -1.09567500 2.02569900C 1.87192400 -0.34561000 -0.10439600C 2.93545200 -1.11789000 -0.58830800C 2.17912300 0.87621300 0.50203200C 4.23707100 -0.67931700 -0.49924800H 2.72181800 -2.07246300 -1.04786700C 3.48892800 1.30700900 0.59413400H 1.40281400 1.47175400 0.95143700C 4.52377200 0.54343300 0.08742900H 5.03461200 -1.29289500 -0.89033700H 3.69965300 2.25117300 1.07348700H 5.54287100 0.89160900 0.15399200

MCb

E(RmPW+HF-B95) = -1163.98860718 a.u.

C -2.95173400 0.60653300 -0.55909500C -2.03213500 -1.44982200 -1.06296400C -1.02796100 -0.44377500 -1.24201500C 0.39358700 -1.19884700 1.24691500C 0.19492400 -0.06702800 1.92066200C -0.89142600 1.84851100 -0.43797600N -1.48394100 0.72277100 -0.76850700H 0.00623500 -0.62213600 -1.44822000O -1.91071000 -2.65795600 -1.11147300N -3.20104500 -0.78261900 -0.76351300C -4.27740400 -1.44365500 -0.08796000H -4.26892800 -1.22038500 0.97985600H -5.24068000 -1.16268900 -0.50936400H -4.12771500 -2.50866700 -0.23080900H -1.52044100 2.55767700 0.07435700C 0.51138300 2.14078200 -0.58108200C 1.08435200 3.01235000 0.35282700C 1.33012900 1.61959400 -1.58375100C 2.42518700 3.32336900 0.30396400H 0.46188800 3.41721400 1.13844200C 2.67303800 1.94592800 -1.63466300H 0.91042500 0.99390600 -2.35477100C 3.23119700 2.78697600 -0.68994600H 2.84631200 3.98830500 1.04305500H 3.28601600 1.53690900 -2.42348800H 4.28130200 3.03245500 -0.73109800C -3.69065200 1.49043000 -1.53489500H -3.45901400 2.53980600 -1.37087100H -3.42054400 1.21545800 -2.55069800H -4.76101100 1.34910900 -1.40769800H -3.15482300 0.88820600 0.47497200

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H -0.46203500 -1.84154000 1.09445800C 1.65350900 -1.64464600 0.68443700C 1.66697400 -2.84947300 -0.01452800C 2.83093800 -0.90481300 0.78552000C 2.83849100 -3.31916800 -0.57638300H 0.74214300 -3.39540300 -0.13583700C 3.99744300 -1.37671000 0.22448400H 2.82955500 0.05457100 1.28210000C 4.00610300 -2.58812300 -0.45054100H 2.83754800 -4.25313800 -1.11667300H 4.90357400 -0.79628900 0.30616700H 4.92254800 -2.95452600 -0.88781100H 0.91781800 0.68695700 2.16793200N -1.12265700 0.29176200 2.32201500O -1.25486100 1.36638500 2.87188400O -2.04346800 -0.46589100 2.07683600

TSmn-b

E(RmPW+HF-B95) = -1163.979447 a.u.

C 2.73728200 -0.79746700 -0.62196900C 1.99695200 1.36976700 -1.01315600C 0.83215600 0.50360300 -0.91499300C -0.01356100 1.01261500 1.06849600C -0.03620800 -0.19377400 1.71994100C 0.55200700 -1.75659200 -0.17313100N 1.26058800 -0.75526700 -0.66455200H -0.11193400 0.71862200 -1.37146100O 2.01517600 2.57446700 -1.13113300N 3.08927500 0.56687900 -0.84583600C 4.37257300 1.08819000 -0.48604600H 4.59071600 0.89539000 0.56471200H 5.16135100 0.66108800 -1.10222900H 4.33421000 2.15927800 -0.65333100H 1.13308800 -2.55159700 0.27215400C -0.84453000 -2.01259200 -0.47375800C -1.57631000 -2.81056800 0.40796300C -1.47331600 -1.52903900 -1.61711000C -2.90966100 -3.07099800 0.17637600H -1.08919500 -3.19498900 1.29357800C -2.80960000 -1.79693100 -1.84779800H -0.91225900 -0.96427700 -2.34502600C -3.53591200 -2.55568900 -0.94923900H -3.46510600 -3.67732000 0.87545000H -3.28268700 -1.41170600 -2.73798800H -4.58091600 -2.75676200 -1.12799200C 3.26324200 -1.72556700 -1.69152300H 2.94644800 -2.74926500 -1.50573700

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H 2.90548000 -1.41007900 -2.66792500H 4.35029100 -1.70102000 -1.69196100H 3.04354300 -1.12046400 0.37106900H 0.85366300 1.63344300 1.23506600C -1.23126500 1.71300800 0.64819800C -1.12296400 3.04628500 0.26266400C -2.48000700 1.09968900 0.59100900C -2.23643500 3.75703600 -0.14079000H -0.14868300 3.51221700 0.26005800C -3.59166600 1.81325600 0.18885700H -2.58907000 0.05703300 0.85320800C -3.47654300 3.14513700 -0.17314600H -2.13317200 4.79092200 -0.43314300H -4.55361500 1.32440400 0.15518100H -4.34849400 3.69925800 -0.48608600H -0.90610800 -0.76518100 1.97734200N 1.12937400 -0.65426700 2.35447200O 1.04879600 -1.65186700 3.05042800O 2.17982500 -0.05342800 2.15463000

TSmx-b

E(RmPW+HF-B95) = -1163.975194a.u.

C 0.89195200 1.74106300 -0.91334900C 1.39509700 1.33053900 1.31943000C 0.11409100 0.71865900 1.00309700C 0.64939200 -1.38312400 0.54220700C -0.37586300 -1.73861300 -0.29995300C -1.27624800 0.63818900 -0.94836300N -0.23988900 1.08019200 -0.24839200H -0.61681900 0.39888000 1.72104600O 2.01557900 1.28252000 2.35629400N 1.82751200 1.89832100 0.15330800C 3.19230500 2.26573100 -0.06397600H 3.66478000 1.60564500 -0.79177600H 3.28118200 3.29703200 -0.40189700H 3.69924200 2.16131800 0.88949200H -1.15422500 0.71794000 -2.01926400C -2.62960700 0.50323100 -0.45902800C -3.56186500 -0.13123900 -1.28078000C -3.06707700 1.04585800 0.75006100C -4.88513400 -0.22469800 -0.90536700H -3.23461000 -0.56200700 -2.21521900C -4.39285600 0.95722400 1.11601200H -2.37571300 1.57206600 1.38924600C -5.30637100 0.31840000 0.29465100H -5.58792000 -0.72907400 -1.55011700H -4.71551500 1.39038700 2.05029300

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H -6.34134900 0.24339300 0.59068800C 0.46959200 3.05726900 -1.52185800H -0.26627500 2.90764600 -2.30792400H 0.04552300 3.69791000 -0.75369400H 1.33369000 3.55342600 -1.95703400H 1.28702200 1.06921100 -1.67937900C 2.04341500 -1.32627400 0.09360200C 3.05758300 -1.27060700 1.04703700C 2.40676700 -1.34283300 -1.25251700C 4.38624800 -1.23818400 0.67029800H 2.79421700 -1.23879800 2.09267500C 3.73531400 -1.31360300 -1.62944000H 1.64492000 -1.39631400 -2.01658000C 4.73245300 -1.26247900 -0.66883400H 5.15328200 -1.19782100 1.42844600H 3.99407600 -1.34179800 -2.67737300H 5.77058100 -1.24632400 -0.96397600H 0.49294900 -1.56927600 1.59353500N -1.61214200 -2.10282300 0.25530600O -2.40688700 -2.67613000 -0.46767600O -1.84508500 -1.79394100 1.41486300H -0.28138300 -2.02991500 -1.32817400

TSon-b

E(RmPW+HF-B95) = -1163.972694 a.u.

C 2.50586800 1.09585200 -0.93566800C 2.83587900 0.31585000 1.23222200C 1.40298600 0.40207400 0.96340400C 0.69670100 -1.69629700 0.31118000C -0.29113000 -1.42547000 -0.60706000C 0.05241300 0.93714800 -0.93266500N 1.21126900 0.90843100 -0.25591400H 0.64388000 0.40277200 1.71943900O 3.38129000 -0.05858500 2.24000300N 3.43892600 0.66468500 0.05654600C 4.78347800 0.28367100 -0.25721200H 5.36105900 1.12762300 -0.62951700H 5.23090300 -0.07341000 0.66401100H 4.78901100 -0.52042600 -0.99249600H 0.18307900 1.03146600 -2.00147600C -1.18296400 1.46769500 -0.38573400C -2.33382200 1.40086100 -1.17183300C -1.28173000 2.05762300 0.87249700C -3.54231400 1.86963300 -0.70470900H -2.27367100 0.95562700 -2.15425500C -2.49400800 2.53023400 1.33705200H -0.40223500 2.18419800 1.48441900

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S28

C -3.63271000 2.42657900 0.56019100H -4.42040000 1.79263200 -1.32755500H -2.54461200 2.98822700 2.31341200H -4.57990200 2.78761900 0.93017200C 2.68503700 2.54617800 -1.32034800H 1.92339800 2.85054500 -2.03454900H 2.62082200 3.17727200 -0.43820100H 3.65998300 2.68456700 -1.78151500H 2.53583000 0.44851600 -1.80950900C -1.69965400 -1.50200100 -0.25251600C -2.64385400 -1.83150800 -1.22037500C -2.14657300 -1.23525700 1.04054600C -3.98699300 -1.90882300 -0.90525400H -2.31397700 -2.04002100 -2.22836200C -3.48829000 -1.30131100 1.35393000H -1.43560700 -0.95830300 1.80581700C -4.41527500 -1.64086600 0.38233900H -4.70109900 -2.17884200 -1.66865800H -3.81373500 -1.08348700 2.35971200H -5.46463400 -1.69542700 0.62879600H -0.02800800 -1.54656900 -1.64609100H 0.52863200 -2.06058600 1.30805800N 1.98335900 -2.06122000 -0.17555200O 2.27051600 -1.76796100 -1.32831800O 2.73921000 -2.62451000 0.58367300

TSox-b

E(RmPW+HF-B95) = -1163.966730 a.u.

C -1.37223700 -1.09548700 -1.47256700C -1.05931400 -2.66003300 0.21932600C 0.09168200 -1.76836000 0.18176200C -0.15546600 -0.05473200 1.83070900C -0.04006100 1.07986500 1.07701400C 0.60509400 0.23992000 -1.02532600N -0.06884600 -0.89603800 -0.81858700H 1.04481700 -1.97983800 0.62413100O -1.26078100 -3.61621500 0.92660900N -1.94278700 -2.14610000 -0.69620800C -3.20248400 -2.75751700 -0.97937200H -3.21437100 -3.24918200 -1.95214800H -3.36207800 -3.50599500 -0.20995200H -4.00936700 -2.02700000 -0.94422700H 0.10123700 0.92823900 -1.68914300C 2.05491500 0.34892000 -0.94342700C 2.62951000 1.61839300 -0.98317300C 2.89734100 -0.75730800 -0.90111700C 3.99861800 1.77714500 -0.94621700

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S29

H 1.98667800 2.48615700 -1.04343100C 4.26765400 -0.59632700 -0.86748000H 2.48680000 -1.75440800 -0.92317100C 4.82590800 0.66881600 -0.87990300H 4.42280400 2.76938200 -0.97009300H 4.90342900 -1.46776600 -0.83308700H 5.89729400 0.79137200 -0.84437900C -1.17563200 -1.45314100 -2.92859400H -0.66842600 -0.64602400 -3.45121800H -0.58145700 -2.35951300 -3.01252600H -2.13828600 -1.61456400 -3.40735100H -1.94524600 -0.17186000 -1.37997300N 0.97936200 -0.51762600 2.56067600O 0.76488300 -1.25623000 3.49705700O 2.08687500 -0.17483800 2.19276800H -1.06943400 -0.44952100 2.23400600H 0.91389900 1.58355700 1.09340800C -1.20483900 1.84613000 0.64026700C -1.04325000 3.16348100 0.21647400C -2.49200400 1.30895200 0.63177600C -2.12348300 3.91698900 -0.19912900H -0.05503700 3.60153700 0.22986900C -3.57225000 2.06265400 0.21506900H -2.65055400 0.28722500 0.94778100C -3.39497300 3.37019100 -0.20319500H -1.97244800 4.93798300 -0.51566200H -4.56020900 1.62702500 0.22230200H -4.24034000 3.95850500 -0.52515100

12n-b

E(RmPW+HF-B95) = -1164.06784683 a.u.

C -2.50143800 1.13288300 -0.64817800C -2.29311100 -1.18782000 -0.78874900C -0.89798000 -0.62604200 -0.70747000C -0.15062500 -1.08987900 0.56530600C -0.03474500 0.17390300 1.39848800C -0.26565500 1.34772900 0.41578700N -1.08229700 0.80557700 -0.63534800H -0.33635600 -0.93333700 -1.58983900O -2.58208000 -2.36131200 -0.79954500N -3.13852000 -0.14161100 -0.84481400C -4.55860100 -0.30748400 -0.79345900H -4.95833100 0.07144100 0.14696000H -5.04711500 0.20382400 -1.62026300H -4.75932800 -1.37136600 -0.86161000H -0.79739100 2.15509300 0.92233400C 1.06166300 1.88181300 -0.06768800

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S30

C 1.92529800 2.48207700 0.83986300C 1.44648800 1.75924300 -1.38989800C 3.16047400 2.94502500 0.42965500H 1.62568400 2.58769600 1.87456000C 2.68643000 2.21983000 -1.80066800H 0.76374000 1.30682700 -2.09162200C 3.54627200 2.80971900 -0.89424900H 3.82209500 3.41367000 1.14232000H 2.97993900 2.11378700 -2.83402700H 4.51262800 3.16746200 -1.21542300C -2.83718300 2.12514900 -1.73744500H -2.28914100 3.04993100 -1.57376500H -2.55291500 1.71977100 -2.70505600H -3.90012900 2.35940100 -1.74558400H -2.80899000 1.54096100 0.32089200H -0.80084700 -1.78845200 1.08734000C 1.13037500 -1.81621700 0.25160600C 1.00506800 -3.11326300 -0.23610600C 2.39786600 -1.27129300 0.37955800C 2.12053100 -3.85136400 -0.57678300H 0.01542700 -3.53423700 -0.35300100C 3.51729200 -2.01355500 0.04033400H 2.53330900 -0.26142100 0.73548800C 3.38432500 -3.30337100 -0.43563500H 2.00324300 -4.85773600 -0.94932100H 4.49719800 -1.57359400 0.14798100H 4.25925800 -3.87889400 -0.69732700H 0.87618900 0.26868000 1.97398700N -1.12417500 0.24927500 2.40670100O -0.86980500 0.81138500 3.44222700O -2.20807600 -0.19191000 2.09901700

12x-b

E(RmPW+HF-B95) = -1164.06184489 a.u.

C 0.51446400 1.88148800 -0.65192700C 1.79729300 1.34990100 1.22853200C 0.57931000 0.46876900 1.24865500C 0.82325700 -1.01601500 0.90113200C -0.49114900 -1.37893600 0.22231100C -0.96654000 -0.07843600 -0.47712800N -0.26134400 0.98929400 0.19366700H 0.09412300 0.52987100 2.21779200O 2.70105400 1.35016800 2.03115700N 1.68830800 2.13645200 0.13945700C 2.72686300 3.03321200 -0.26299500H 3.12735100 2.75208500 -1.23669800H 2.37074000 4.06045100 -0.30958600

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S31

H 3.51286300 2.96158800 0.48131900H -0.62072600 -0.14987500 -1.51232900C -2.46416800 0.08003200 -0.52421500C -3.19624400 -0.67349300 -1.43060100C -3.12456700 0.93571400 0.33986800C -4.57241600 -0.56974700 -1.47807700H -2.68467500 -1.34661200 -2.10538900C -4.50349400 1.04226400 0.29037700H -2.54331300 1.51494400 1.04026600C -5.22913000 0.29166400 -0.61663300H -5.13225900 -1.15949200 -2.18779700H -5.01220700 1.71318200 0.96588500H -6.30455200 0.37698200 -0.65296300C -0.25213800 3.13649700 -0.99601900H -1.17221800 2.87128000 -1.51196100H -0.50962200 3.66875300 -0.08385200H 0.32541200 3.79102900 -1.64610000H 0.81109500 1.37357400 -1.58243700C 2.02481300 -1.23965900 0.01537500C 3.28060000 -1.29780300 0.61204000C 1.94798300 -1.36986700 -1.36405700C 4.41916400 -1.47748300 -0.14787200H 3.36116100 -1.17577200 1.68120400C 3.08851600 -1.55196100 -2.12846400H 0.99449600 -1.34975400 -1.86933600C 4.32826300 -1.60545000 -1.52329500H 5.38188800 -1.51863200 0.33820000H 3.00092000 -1.65698900 -3.19929000H 5.21818100 -1.74909200 -2.11683800H 0.94737900 -1.59265500 1.81457500N -1.50101400 -1.81344200 1.21880100O -2.18893900 -2.75484600 0.91879700O -1.58845400 -1.17679200 2.24168100H -0.42105700 -2.21336000 -0.46324500

13n-b

E(RmPW+HF-B95) = -1164.06610501 a.u.

C 1.96877500 1.56242500 0.28480400C 2.88764800 -0.49827000 0.87591300C 1.40048600 -0.68931000 0.72719300C 0.93828500 -1.60928600 -0.38389400C -0.39102800 -0.96169100 -0.79917100C -0.05851600 0.54141900 -0.67962400N 0.85935100 0.62672400 0.44586800H 1.01273700 -1.10142500 1.66014500O 3.69649500 -1.36763600 1.08922000N 3.11055100 0.82437700 0.76351500

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S32

C 4.43804500 1.35774500 0.71820900H 4.55827700 2.17593000 1.42452700H 5.11610300 0.55303300 0.98147100H 4.67939400 1.71314300 -0.28369800H 0.47774700 0.80387500 -1.59725700C -1.26402200 1.43947900 -0.60382600C -2.03526500 1.60212000 -1.74655300C -1.63526800 2.10620700 0.55186500C -3.16328700 2.39872300 -1.73241900H -1.74555600 1.10120700 -2.66059800C -2.76086800 2.91249800 0.56687700H -1.02944300 1.99124200 1.43791000C -3.53024100 3.05815600 -0.57181600H -3.75261400 2.51174300 -2.62976100H -3.03628900 3.42752500 1.47500800H -4.40800500 3.68619100 -0.55825600C 1.76204200 2.85328700 1.03913100H 0.89105600 3.37362000 0.65103500H 1.60988800 2.64711500 2.09589400H 2.62131900 3.51152700 0.92551900H 2.11272300 1.78101200 -0.78168400C -1.50969500 -1.48083700 0.06246700C -2.36603300 -2.44589900 -0.44940800C -1.69308200 -1.05593800 1.37193600C -3.37903700 -2.97877100 0.32606200H -2.23825600 -2.78260800 -1.46864000C -2.70456200 -1.58821200 2.14919900H -1.05421700 -0.28673800 1.77764600C -3.54983000 -2.55213800 1.63023900H -4.03649100 -3.72594100 -0.09177300H -2.83558000 -1.24302700 3.16349400H -4.34082100 -2.96516800 2.23737500H -0.61898100 -1.20899700 -1.83420200H 0.84588700 -2.65010000 -0.10556400N 1.85175700 -1.59215500 -1.55460500O 2.43702000 -0.55907000 -1.79742300O 1.90301300 -2.59279800 -2.21994300

13x-b

E(RmPW+HF-B95) = -1164.06542739 a.u.

C 1.12078700 1.25186200 -1.52315300C 1.50578600 1.93872300 0.67400000C 0.07679900 1.46028700 0.59949000C -0.13973600 0.23757200 1.47633800C -0.06481400 -0.94499000 0.52821100C -0.62998900 -0.31411600 -0.76856300N -0.11546100 1.04218600 -0.77724800

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S33

H -0.59275500 2.25869400 0.91224000O 2.08768300 2.27819900 1.67890300N 2.00519600 1.87326100 -0.57064400C 3.38733700 2.11931800 -0.84692900H 3.50686100 2.84202300 -1.65070000H 3.83130600 2.51474600 0.06050800H 3.89330900 1.19258400 -1.11986600H -0.24969100 -0.84295300 -1.64166500C -2.13865800 -0.36246900 -0.79969100C -2.76924700 -1.60012600 -0.81724000C -2.91194800 0.78511600 -0.80547800C -4.14538700 -1.69109000 -0.84225600H -2.17389900 -2.50418100 -0.81377500C -4.29436000 0.69587600 -0.82246800H -2.42112300 1.74593500 -0.80708200C -4.91385200 -0.53833800 -0.84111500H -4.62083000 -2.66001100 -0.85826700H -4.88677200 1.59827000 -0.81920900H -5.99103900 -0.60536100 -0.85274500C 0.89374100 2.10468100 -2.74920500H 0.18403300 1.61108500 -3.40815900H 0.48200800 3.06721900 -2.45719500H 1.81779500 2.26205300 -3.30254100H 1.55259100 0.29008700 -1.82284900N -1.47263300 0.27460900 2.17963900O -1.90432000 -0.78021800 2.56948300O -1.98409200 1.34791600 2.36830500H 0.56440300 0.20516800 2.30351600H -0.71053300 -1.73804300 0.89493100C 1.31983800 -1.50907100 0.31640100C 1.43901900 -2.58595800 -0.55876000C 2.47013100 -1.03795500 0.93172500C 2.66193200 -3.16954400 -0.81802400H 0.55045500 -2.97803300 -1.03616300C 3.70181400 -1.61907800 0.66857900H 2.43667200 -0.20970400 1.62284700C 3.80475500 -2.68258100 -0.20525300H 2.72337700 -4.00763300 -1.49562800H 4.58190700 -1.23373100 1.16076900H 4.76437400 -3.13449400 -0.40437500

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S34

11a

E(RmPW+HF-B95) = -767.939676654 a.u.

C -1.54618200 -0.30735200 -0.56400700C -0.34941300 1.47232700 0.25331900H -1.58570900 -0.66814200 -1.59439400H 0.47695000 2.11283200 0.47758000C -1.70586900 1.89718500 0.12748200O -2.19501500 2.98497400 0.33326900N -0.19464000 0.27584300 -0.33298400C 0.86791700 -0.41792200 -0.67419400H 0.66781600 -1.26275000 -1.31004900N -2.42106100 0.80224600 -0.36539100C -3.52915400 1.05597900 -1.24354300H -4.34440900 0.35668900 -1.08114700H -3.87710800 2.05901500 -1.01918600H -3.23327900 1.00972900 -2.29489300C -1.83827000 -1.47753300 0.40651000C -1.03932400 -2.72621200 0.06076900C -1.55015100 -1.05795000 1.83693900C -3.31966600 -1.80514400 0.26865800H -1.13079600 -2.98468100 -0.99533500H 0.01463600 -2.62371700 0.30250900H -1.42418900 -3.56638400 0.63579500H -2.09545100 -0.15155400 2.09225300H -1.85987600 -1.84612100 2.52115900H -0.48736400 -0.87895400 1.99147700H -3.55567000 -2.68268500 0.86736700H -3.93520600 -0.98168500 0.62010500H -3.59038500 -2.02789800 -0.76423500C 2.23364600 -0.13119600 -0.33148400C 3.23475700 -0.71701100 -1.11497700C 2.62995100 0.64172300 0.76393200C 4.56812700 -0.51485100 -0.83731400H 2.94872100 -1.33125700 -1.95689800C 3.96943600 0.83378700 1.04166900H 1.89245700 1.05611500 1.43109700C 4.94571200 0.26975900 0.24112000H 5.31912800 -0.97050500 -1.46483600H 4.25051700 1.42904400 1.89735600H 5.99013800 0.43295400 0.45746400

MCa

E(RmPW+HF-B95) = -1281.85835061 a.u.

C -2.57443600 -0.11085600 0.01939000C -1.29414800 -1.92429800 -0.61245000

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S35

C -0.57217400 -0.72944600 -0.91281600C 1.32987800 -1.17255800 1.27040900C 1.08861100 -0.04565600 1.93844300C -0.77071400 1.50597900 0.01771900N -1.18546400 0.30608100 -0.31877600H 0.44224800 -0.69210300 -1.24825700O -0.91377600 -3.07697100 -0.69344600N -2.52274500 -1.53620600 -0.10444500C -3.18425600 -2.39679800 0.84135100H -3.04462900 -2.03875300 1.86078300H -4.24705000 -2.48500200 0.63487800H -2.72675600 -3.37554800 0.74063800H -1.43028000 2.03937700 0.68040800C 0.49176500 2.10873900 -0.31782800C 0.95614200 3.12288600 0.52959300C 1.27355300 1.76214200 -1.42074800C 2.16663800 3.73794000 0.30133100H 0.36409000 3.39169800 1.39304600C 2.48400200 2.39078500 -1.64835200H 0.92076600 1.03416200 -2.13229600C 2.94308900 3.37104900 -0.78877500H 2.50939500 4.50788400 0.97605200H 3.07024500 2.10955100 -2.51002600H 3.89159700 3.85336200 -0.96849700C -3.61060500 0.54509000 -0.92008000H -2.76648100 0.17927400 1.05296100H 0.57554000 -1.94566900 1.30813100C 2.50989100 -1.44886200 0.47179900C 2.50663200 -2.59753800 -0.31665700C 3.61450000 -0.59967900 0.43119800C 3.59038800 -2.89570300 -1.12041100H 1.62914800 -3.22899100 -0.32058100C 4.69541700 -0.90404600 -0.36768000H 3.62386500 0.30639300 1.01869200C 4.68766200 -2.05424400 -1.14249200H 3.57464900 -3.78444700 -1.73223300H 5.54775200 -0.24242700 -0.39046300H 5.53648100 -2.28852700 -1.76701200H 1.71457600 0.82371000 2.00584200N -0.15568400 0.13645100 2.60378500O -0.31999000 1.19923900 3.16894800O -0.99015400 -0.74846300 2.55890100C -3.22649900 0.33332300 -2.37378900H -3.05447900 -0.72138000 -2.57902100H -4.03069000 0.67951000 -3.02098900H -2.32673300 0.88761600 -2.63493700C -4.94352400 -0.14060500 -0.65005700H -5.20563400 -0.11300500 0.40804400H -5.73356800 0.36627200 -1.20064900H -4.91802200 -1.17721500 -0.97465000

Page 36: Supplementary Material10.1007... · Web viewP9, d(C1 C5) = 1.687 Å and d(C3 C4) = 2.095 Å, the second most relevant topological change along the reaction path takes place; likewise

S36

C -3.76477500 2.03189000 -0.63434500H -3.94663700 2.22202300 0.42415900H -2.89376800 2.60345500 -0.94378100H -4.61922400 2.41684300 -1.18793500

TSmn-a

E(RmPW+HF-B95) = -1281.84949264 a.u.

C -2.47279200 0.01590100 -0.02330000C -1.31543800 -1.87298400 -0.69710100C -0.39379900 -0.74947600 -0.71250200C 0.90780200 -1.25180300 1.01321000C 0.75562200 -0.17778600 1.85237800C -0.50183700 1.39853500 0.34881300N -1.04092000 0.32901300 -0.20728900H 0.47037800 -0.68001900 -1.34093700O -1.05050000 -3.03649300 -0.90175800N -2.52633800 -1.39538200 -0.25986900C -3.38535100 -2.25913900 0.51026300H -3.33690800 -1.99674000 1.56634100H -4.41564600 -2.21694900 0.17135100H -3.01424000 -3.26931100 0.37385300H -1.15936700 1.94591300 1.00765700C 0.72775300 2.04430600 -0.06745900C 1.35075500 2.89734600 0.84675300C 1.29842600 1.87931900 -1.32574400C 2.53507800 3.52327700 0.52836700H 0.90783400 3.02996200 1.82443600C 2.48378600 2.51671400 -1.64372800H 0.80714000 1.27073500 -2.06879700C 3.11300200 3.32805300 -0.71835400H 3.01237600 4.16601900 1.25215300H 2.91590100 2.37591000 -2.62256900H 4.04222200 3.81665500 -0.96776200C -3.33880700 0.83082400 -1.00795200H -2.75230400 0.24420100 1.00503100H 0.26173300 -2.09961400 1.18121200C 2.16609100 -1.53284100 0.31479600C 2.32331500 -2.78011800 -0.28309600C 3.19076700 -0.59786300 0.19235600C 3.48385600 -3.09492400 -0.96317500H 1.51070800 -3.48960500 -0.23079300C 4.35062800 -0.91657200 -0.48591500H 3.08236900 0.39229600 0.61215100C 4.50457000 -2.16657300 -1.06214900H 3.58867900 -4.06761100 -1.41932700H 5.13672900 -0.18123800 -0.56900700H 5.41278700 -2.41125700 -1.59185000

Page 37: Supplementary Material10.1007... · Web viewP9, d(C1 C5) = 1.687 Å and d(C3 C4) = 2.095 Å, the second most relevant topological change along the reaction path takes place; likewise

S37

H 1.50473600 0.55065000 2.09356700N -0.37026100 -0.10701800 2.68665100O -0.40588800 0.76936200 3.53355000O -1.28388700 -0.90425900 2.50104300C -2.82847200 0.66666200 -2.42923600H -2.74704300 -0.38607700 -2.69491900H -3.51843800 1.13710700 -3.12739400H -1.85419200 1.13450600 -2.56177900C -4.75997100 0.29190400 -0.92065500H -5.12315300 0.27174400 0.10718900H -5.43000000 0.92695900 -1.49679800H -4.81936700 -0.71360200 -1.32889200C -3.34701300 2.30322400 -0.62639100H -3.63369900 2.44764800 0.41579600H -2.38135800 2.77709400 -0.78782400H -4.07085400 2.83352800 -1.24229500

TSmx-a

E(RmPW+HF-B95) = -1281.84341057 a.u.

C 0.95429700 1.54467300 -0.29959900C 1.42978700 0.44389700 1.68952800C 0.11094100 0.04066100 1.24531600C 0.57090500 -1.94372900 0.43743700C -0.53617000 -2.15735700 -0.34730600C -1.15208800 0.38120300 -0.76740800N -0.15954000 0.65058600 0.07158800H -0.65436200 -0.40126600 1.85688400O 2.04948800 0.02731200 2.64124000N 1.92645000 1.27943500 0.71685600C 3.34438000 1.32564700 0.47551400H 3.58228000 0.87680500 -0.48874400H 3.73780100 2.33712800 0.50758100H 3.81360800 0.74212500 1.26061600H -0.93718600 0.65053600 -1.79155800C -2.54568800 0.20298500 -0.43623500C -3.42351400 -0.09516600 -1.48190600C -3.07494100 0.38439400 0.84218800C -4.77808600 -0.20239600 -1.26138700H -3.02640700 -0.24504400 -2.47555000C -4.43491000 0.28298900 1.05501600H -2.42995200 0.63555800 1.66866700C -5.29133800 -0.01172800 0.01023600H -5.43635900 -0.43842500 -2.08317200H -4.82603900 0.43296200 2.04942900H -6.35238700 -0.09768500 0.18632600C 0.47845300 3.01691600 -0.32852300H 1.33617200 1.26120400 -1.28422100

Page 38: Supplementary Material10.1007... · Web viewP9, d(C1 C5) = 1.687 Å and d(C3 C4) = 2.095 Å, the second most relevant topological change along the reaction path takes place; likewise

S38

C 1.89207300 -1.81594200 -0.17616600C 3.03241600 -2.09364700 0.57346100C 2.05072000 -1.44253300 -1.51057000C 4.28676900 -2.04364300 -0.00404600H 2.92467800 -2.35356300 1.61511200C 3.30591900 -1.38862900 -2.08618500H 1.18164200 -1.20678300 -2.10818200C 4.42910800 -1.69820100 -1.33671800H 5.15675200 -2.27858900 0.59014000H 3.40743800 -1.11427200 -3.12557500H 5.40854300 -1.66849000 -1.78933900H 0.53584900 -2.28149200 1.46215900N -1.75295400 -2.47750200 0.26878600O -2.66701600 -2.85208200 -0.44053200O -1.85056700 -2.31819100 1.48003400H -0.54230400 -2.32479500 -1.40669200C 1.70995200 3.90409500 -0.44701100H 1.40250000 4.93179600 -0.62960200H 2.29311100 3.89164700 0.46959600H 2.35341800 3.60039000 -1.27352500C -0.26497200 3.35310900 0.95299000H 0.33374100 3.10501500 1.82808800H -0.48190600 4.41917400 0.98638000H -1.21176600 2.81882200 1.01439400C -0.42195600 3.27755000 -1.52834300H 0.04236300 2.95159200 -2.46020800H -1.39086300 2.79376700 -1.43498100H -0.60563400 4.34706000 -1.61229700

12n-a

E(RmPW+HF-B95) = -1281.93884596 a.u.

C -2.37289400 0.09481000 -0.03975500C -1.43595900 -1.96693500 -0.61058200C -0.30894700 -0.97415000 -0.57925600C 0.73453800 -1.32462600 0.51078300C 0.55469700 -0.23040600 1.54664500C -0.18135500 0.91623900 0.81541800N -0.93716400 0.27562900 -0.22540400H 0.17908000 -0.94119200 -1.55373300O -1.31953500 -3.15849400 -0.77726600N -2.58087800 -1.29236100 -0.38043900C -3.77919400 -2.02129200 -0.06960300H -4.25408400 -1.59578400 0.81133000H -4.48958400 -2.01681700 -0.89280900H -3.49122800 -3.04837800 0.13184700H -0.85485100 1.42842300 1.50405700C 0.82765000 1.91471900 0.30143500

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S39

C 1.57216300 2.65349200 1.21240600C 1.05123200 2.08605700 -1.05278100C 2.53156300 3.54454200 0.77364300H 1.39566100 2.52865100 2.27290600C 2.01554700 2.97746400 -1.49333800H 0.45964600 1.51922500 -1.75559500C 2.75889000 3.70483900 -0.58395900H 3.10144300 4.11667800 1.48996400H 2.18628200 3.09944500 -2.55214500H 3.51103000 4.39807300 -0.92837400C -3.17506000 1.09912300 -0.88469700H -2.64836600 0.24260500 1.01343400H 0.43788500 -2.27371000 0.95212700C 2.12024200 -1.50543200 -0.05164900C 2.33668800 -2.65455000 -0.80554700C 3.16267400 -0.60642300 0.10744200C 3.56819700 -2.90373000 -1.37716300H 1.51922800 -3.35060100 -0.94074100C 4.39978800 -0.85925700 -0.46275100H 3.02784200 0.30773500 0.66514100C 4.60843100 -2.00587300 -1.20298900H 3.71788100 -3.80335300 -1.95475700H 5.20085500 -0.14859100 -0.32651000H 5.57419500 -2.20026700 -1.64418600H 1.45711100 0.09263000 2.04689700N -0.34079900 -0.67063800 2.64812400O -0.13934200 -0.19062700 3.73554000O -1.24983000 -1.42015200 2.37351800C -2.89439600 0.87908600 -2.35912600H -3.19937000 -0.11775000 -2.67367000H -3.43710200 1.60476700 -2.96267500H -1.83200500 0.99423000 -2.56734700C -4.66597800 0.96857900 -0.60701200H -4.87613600 0.99028000 0.46305700H -5.19970700 1.80139400 -1.06189900H -5.08510900 0.05441800 -1.01760900C -2.73367200 2.49782200 -0.47749700H -2.89799700 2.67131700 0.58762500H -1.68051500 2.66332700 -0.69558500H -3.30962100 3.24442200 -1.02145300

12x-a

E(RmPW+HF-B95) = -1281.92981969 a.u.

C -1.14407500 1.87547800 -0.49309600C 0.74573200 1.98053000 0.89529000C 0.21402100 0.57663600 0.99443400C 1.10887300 -0.54906800 0.41317300

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S40

C 0.45257800 -0.76812100 -0.92987200C -1.04719700 -0.57212700 -0.64195600N -1.01005600 0.60079200 0.20459900H 0.01998000 0.36838500 2.04553200O 1.68883900 2.43960100 1.48946900N -0.03007600 2.64132000 0.00590100C 0.29319100 3.98735900 -0.36516600H 0.13213200 4.13452800 -1.43036000H -0.29480900 4.72028700 0.18511800H 1.33989600 4.14315600 -0.12351800H -1.57306600 -0.34705400 -1.56695000C -1.70916900 -1.75445900 0.01979100C -1.97205400 -2.90422800 -0.71549400C -2.08608500 -1.71071400 1.35334600C -2.58321800 -3.99139000 -0.12225600H -1.70064900 -2.95078700 -1.76081800C -2.69876600 -2.80065500 1.94718100H -1.92279100 -0.80606000 1.91837400C -2.94590200 -3.94436300 1.21281300H -2.77936500 -4.87713600 -0.70681800H -2.98806100 -2.75028700 2.98601700H -3.42506200 -4.79410500 1.67469900C -2.53694700 2.49233500 -0.25585400H -1.02887700 1.73138100 -1.57818200C 2.59261400 -0.33857200 0.34205500C 3.43684400 -1.16673300 1.06403600C 3.15312200 0.63144100 -0.47912900C 4.81007100 -1.02306500 0.98212700H 3.01170000 -1.93931600 1.68800600C 4.52282300 0.77658700 -0.56633200H 2.51475700 1.28920100 -1.05366400C 5.35637900 -0.05012400 0.16687400H 5.45207400 -1.67750000 1.55185000H 4.94146500 1.53889300 -1.20549700H 6.42766600 0.06293900 0.09902200H 0.92009800 -1.44472500 1.00110700N 0.75235400 -2.07496100 -1.54444600O 0.52317000 -2.16164000 -2.72994600O 1.14347200 -2.96898100 -0.84065400H 0.76457900 -0.03360600 -1.66731100C -2.76696600 3.70435600 -1.15002300H -3.81682600 3.99018400 -1.11434900H -2.19039100 4.57252300 -0.84678800H -2.52696300 3.48094100 -2.19027000C -2.68573400 2.86479000 1.20698000H -1.98470600 3.64739100 1.49415600H -3.69261200 3.22647100 1.40777200H -2.50629600 1.99584600 1.83817900C -3.57425200 1.44022700 -0.62674400H -3.47106500 1.13060900 -1.66827200

Page 41: Supplementary Material10.1007... · Web viewP9, d(C1 C5) = 1.687 Å and d(C3 C4) = 2.095 Å, the second most relevant topological change along the reaction path takes place; likewise

S41

H -3.49228600 0.55831600 0.00450700H -4.57521500 1.85091000 -0.50793000