11154

J. Am. Chem. Soc. 2000, 122, 11154-11161

Behavior of Ylides Containing N, O, and C Atoms as Hydrogen Bond

Acceptors
Isabel Rozas,* Ibon Alkorta, and Jose Elguero
Contribution from the Instituto de Qumica Me dica (CSIC), Juan de la CierVa, 3, 28006-Madrid, Spain
ReceiVed May 22, 2000. ReVised Manuscript ReceiVed August 31, 2000

Abstract: The hydrogen bond (HB) basicity of a series of ylides containing nitrogen, oxygen, or carbon as
heavy atoms, as well as the influence of the formation of the HB complexes on their structure, has been
studied. In addition, in this paper we propose the formation of some rather strong HBs (that could be considered
low-barrier hydrogen bonds, LBHBs) between ylides and different neutral molecules. The ylides chosen for
the study were H3N+-N-H, Me3N+-N-H, H2O+-N-H, Me2O+-N-H, H2O+-O-, Me2O+-O-, and Me3N+C-H2. As HB donors, classical donors such as HF, HCN, and HCCH were used. The analysis of the protonation
energies of the ylides and the optimized geometries, interaction energies, and characteristics of the electron
density of the complexes shows that these ylides are very good HB acceptors, forming stable complexes even
with weak HB donors. With strong donors, when the proton transfer did not take place, very strong HBs were
formed with quite large interaction energies and very short HB distances which could be considered as LBHBs.
Moreover, we have found that the sign of the Laplacian of the electron density at the bond critical point
(2FBCP) and that of the energy density (HBCP) could characterize the strength of HBs. Thus, weak HBs (EI <
12.0 kcal/mol) show both 2FBCP and HBCP > 0, and medium HBs (12.0 < EI < 24.0 kcal/mol) show 2FBCP
> 0 and HBCP < 0, while strong HBs (and therefore LBHBs; EI > 24.0 kcal/mol) show both 2FBCP and HBCP
< 0.

Introduction
Ylides as hydrogen bond (HB) acceptors have been the
subject of a number of studies showing a high HB basicity and
finding, in some cases, rather strong HB interactions.1-3 The
HB complexes formed with these specific acceptors can show
low-barrier hydrogen bond (LBHB) interactions which are
particularly short and strong interactions and which have been
the focus of a great deal of attention.4
Platts and Howard theoretically investigated the ability of Ns
C or PsC ylides as HB acceptors with CsH donors.1,2 They
found that CsHC HBs with strengths up to 35 kJ/mol (8.4
kcal/mol) may exist. In the case of the amine and phosphine
oxides as HB acceptors, we have previously found that strong
HBs (>12 kcal/mol) or medium to strong HBs (10 kcal/mol)
can be formed with these ylides, even when weak donors such
as HCCH were considered.3 Moreover, when strong acids were
used as HB donors, a spontaneous proton transfer was observed.
The stability of ylides has been also extensively studied. As
early as 1983, Pople et al. performed a theoretical study of the
isomers and rearrangement barriers of even-electron polyatomic molecules, such as HNC, H2NCH, HOCH, H2NN, H3NCH2, H3NNH, H3NO, H2CC, H3CCH, H3CN, H2COH2,
H2CFH, NOH, HNOH2, HNFH, H2OO, and HFO, many of
* To whom correspondence should be addressed. Fax: 34-91-564 48
53. E-mail: rozas@iqm.csic.es.
(1) Platts, J. A.; Howard, S. T.; Wozniak, K. Chem. Commun. 1996, 63.
(2) Platts, J. A.; Howard, S. T. J. Chem. Soc., Perkin Trans. 2 1997,
2241.
(3) Alkorta, I.; Elguero, J. J. Phys. Chem. 1999, 103, 272.
(4) (a) Garcia-Viloca, M.; Gonzalez-Lafont, A.; Lluch, J. M. J. Phys.
Chem. 1997, 101, 3880. (b) Ramos, M.; Alkorta, I.; Elguero, J.; Golubev,
N. S.; Denisov, G. S.; Benedict H.; Limbach, H.-H. J. Phys. Chem. A 1997,
101, 9791. (c) Kumar, G. A.; McAllister, M. A. J. Am. Chem. Soc. 1998,
120, 3159.

which were described as ylide forms.5 Recently, the stability

of the ylide-like intermediate methyleneoxonium (H2COH2) has
been theoretically studied,6 the possibility of generating the ylide
oxywater (H2OO) has been theoretically calculated at very
high levels of computation,7 and the R2O+-O- ylide structures
of methanol oxide and dimethyl ether oxide have been theoretically studied as a possible new class of stable ylides.8,9 Further,
the chemical bonding in ylides containing hypervalent atoms
has been recently revised by a very accurate analysis of the
corresponding electron density at the ylide bond.9 As well, at
the experimental level, the stability of ylides such as H2CClH,
H2CFH, H2COH2, and H2CNH3 has been studied by neutralization-reionization mass spectrometry.10 Moreover, several crystal
structures of complexes of hydrazinium and 1,1,1-trimethylhydrazinium have been found in the Cambridge Structural
Database11 which could be considered the result of a proton
transfer to the known ylides H3NNH and Me3NNH, respectively.
Despite these preexisting findings, most of these ylides have
not been studied as HB acceptors, nor have the changes in their
electronic nature when the HB complexes are formed been
explored. Therefore, the aim of the present paper is to study
the HB basicity of a series of ylide molecules containing N, O,
(5) Pople, J. A.; Raghavachari, K.; Frisch, M. J.; Binkley, S.; Schleyer,
P. v. R. J. Am. Chem. Soc. 1983, 105, 6389.
(6) Gonzalez, C.; Restrepo-Cossio, A.; Marquez, M.; Wiberg, K. B. J.
Am. Chem. Soc. 1996, 118, 5408.
(7) Huang, H. H.; Xie, Y.; Shaefer, H. F., III. J. Phys. Chem. 1996,100,
6076.
(8) Schalley, C. A.; Harvey, J. N.; Schroder, D.; Schwarz, H. J. Phys.
Chem. A 1998, 102, 1021.
(9) Dobado, J. A.; Martinez-Garcia, H.; Molina Molina, J.; Sundberg,
M. R. J. Am. Chem. Soc. 1998, 120, 8461; 1999, 121, 3156; 2000, 122,
1144.
(10) Wesdemiotis, C.; Feng, R.; Danis, P. O.; Williams, E. R.; McLafferty, F. W. J. Am. Chem. Soc. 1986, 108, 5847.

10.1021/ja0017864 CCC: $19.00 2000 American Chemical Society

Published on Web 11/01/2000

Ylides with N, O, and C Atoms as H Bond Acceptors

J. Am. Chem. Soc., Vol. 122, No. 45, 2000 11155

or C as heavy atoms which have not been previously studied

as HB acceptors, and to analyze how the formation of HB
complexes affects their ylide structure. Moreover, it has been
said that LBHBs would be formed between species when their
pKa values are matched.4c In contrast, however, we propose the
formation of some rather strong HBs (that could be considered
LBHB) between ylides and very different neutral molecules.
The ylides chosen for the present study were H3N+-N-H,
Me3N+-N-H, H2O+-N-H, Me2O+-N-H, H2O+-O-, Me2O+O-, and Me3N+-C-H2. As HB donors, classical strong,
medium, and weak donors such as HF, HCN, and HCCH were
used.
Methods
The geometries of the monomers and the complexes have been fully
optimized with the program Gaussian 9812 using the hybrid method
Becke3LYP13 with the standard 6-31G*14 and 6-311++G**15 basis
sets, and post-Hartree-Fock second-order Mller-Plesset (MP2)16
calculations with the largest basis set. The nature of the monomers
and complexes as a potential energy minimum has been established,
at the B3LYP/6-31G*, in all the cases by verifying that all the
corresponding frequencies were real.
The interaction energies, EI(AB), have been calculated as the
difference between the energy of the complex and the sum of the
energies of the monomers (eq 1):

EI(AB) ) E(AB)AB - [E(A)A + E(B)B]

EI+BSSE(AB) ) EI(AB) + EBSSE(AB)

(3)

The topological properties of the electron density at the bond critical

points (BCPs) have been characterized using the atoms in molecules
(AIM) methodology18 with the AIMPAC program package19 at the MP2/
6-311++G** level, for the isolated ylides and their HB complexes.
The AIM methodology self-consistently partitioned any system and
its properties into its atomic fragments, considering the gradient vector
field of its electron density distribution. From all the criteria proposed
by Koch and Popellier20 on the basis of the AIMs theory to establish
hydrogen bonding, we have chosen the electron density at the bond
critical point (FBCP), its Laplacian (2FBCP), the atomic charges (N),
and the total charge transferred (Q) as the most representative for
this kind of interaction. Moreover, since the energy density at the bond
critical point (HBCP) has proved to be a more sensible and appropriate
index than 2FBCP to characterize the nature of hydrogen bonds,21 we
have also used it in our study. Thus, whereas positive 2FBCP values
are usually associated with ionic bonds or HBs, HBCP can become
negative in some HBs, which demonstrates the real strength of those
bonds.

Results and Discussion

(1)

where E(AB)AB represents the energy of the complex and E(A)A the
energy of the isolated monomer A calculated with its corresponding
basis set.
In addition, a corrected interaction energy (EI+BSSE) excluding the
inherent basis set superposition error (BSSE) has been evaluated. The
BSSE has been calculated using the Boys-Bernardi counterpoise
technique17 and eq 2:

EBSSE(AB) ) E(A)A - E(A)AB + E(B)B - E(B)AB

used to describe the dimer, and E(A)A represents the energy for
monomer A using its geometry in the complex and its basis set.
The corrected interaction energies (EI+BSSE) have been calculated
with eq 3:

(2)

where E(A)AB represents the energy calculated for monomer A using

its geometry in the complex and the complete set of basis functions
(11) For example, see the following. HDRZHO (Hydrazinium hydrogen
oxalate): Ahmed, N. A. K.; Liminga, R.; Olovsson, I. Acta Chem. Scand.
1968, 22, 88. HDRZHO02 (hydrazinium hydrogen oxalate): Thomas J. O.
Acta Crystallogr. B 1973, 29, 1767. HYHYSC (hydrazinium hydrazinedithiocarboxylate): Braibanti, A.; Lanfredi, A. M. M.; Tiripicchio, A.;
Logiudice, F. Acta Crystallogr. B 1969, 25, 93. HYZMAC (hydrazinium
acetate): Hady, S. A.; Nahringbauer, I.; Olovsson, I. Acta Chem. Scand.
1969, 23, 2764. ZZZBNJ02 (hydrazinium L-tartrate): Fun, H.-K.; Sivakumar, K.; Jiang, Y.-Z.; Sun, J.; Zhou, Z.-Y. Acta Crystallogr. C: Cryst.
Struct. Commun.) 1995, 51, 2085. FEXLEZ (N,N,N-trimethylhydrazinium
azide): Habereder, T.; Hammerl, A.; Holl, G.; Klapotke, T. M.; Knizek,
J.; Noth, H. Eur. J. Inorg. Chem. 1999, 849. TMHYZC (1,1,1-trimethylhydrazinium chloride): Giordano, T. J.; Palenik, G. J.; Sisler, H. H. Inorg.
Chem. 1976, 15, 751.
(12) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.;
Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A.
D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi,
M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.;
Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick,
D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.;
Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi,
I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.;
Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson,
B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon,
M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.5; Gaussian,
Inc.: Pittsburgh, PA, 1998.
(13) (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. (b) Lee, C.; Yang,
W.; Parr, R. G. Phys. ReV. B 1988, 37, 785.
(14) Hariharan, P. A.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213.
(15) Krishnam, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J. Chem. Phys.
1984, 80, 3265.
(16) Mller, C.; Plesset, M. S. Phys. ReV. 1934, 46, 618.
(17) Boys, S. B.; Bernardi, F. Mol. Phys. 1970, 19, 553.

Ylides: Geometry, Energy, and Proton Affinity. The

isolated ylides were optimized at the three levels of computation
mentioned above, and their MP2/6-311++G** geometries and
corresponding total energies are shown in Figure 1. The
protonation energy of the ylides studied here (Eprot, kcal/mol)
was evaluated at the MP2/6-311++G** level, and the results
(shown in Table 1) include the B3LYP/6-31G* zero-point
vibrational corrections scaled using the factor reported by Rauhut
and Pulay22 calculated for the monomers. The MP2/6311++G** total energy, the B3LYP/6-31G* ZPE scaled
vibrational correction, and the zero-point corrected energies (au)
for the monomers and protonated species are gathered as
Supporting Information.
In all cases, a large stabilization is observed as a consequence
of the protonation (from 209 to 288 kcal/mol). Overall, these
ylides can be considered bases of high strength in the gas phase
when compared with the experimental protonation affinities of
ammonia (204 kcal/mol) and water (165 kcal/mol). The largest
protonation energy obtained is that of the [Me3N-CH3]+
molecule followed by the non-methylated analogue [H3NCH3]+ (280 kcal/mol). The protonation energy of those molecules in which the protonated atom is a N atom follows the
order [Me3N-NH2]+ > [H3N-NH2]+ > [Me2O-NH2]+ >
[H2O-NH2]+; the protonation energy of those molecules in
which the protonated atom is an O atom follows the order
[Me2O-OH]+ > [H2O-OH]+. The less electronegative atoms
show the largest protonation energies.
The protonation energy is larger for the methylated ylides
([MenX-YHm]+) than for the non-methylated ([HnX-YHm]+).
This increment of protonation energy between the methylated
and non-methylated species increases with the electronegativity
of the protonated atom (Eprot ) 8 kcal/mol for [Z3N-CH3]+
(18) Bader, R. F. W. Atoms in Molecules. A Quantum Theory; Oxford
University Press: New York, 1990.
(19) Bieger-Konig, F. W.; Bader, R. F. W.; Tang, T. H. J. J. Comput.
Chem. 1982, 3, 317.
(20) Koch, U.; Popelier, P. L. A. J. Phys. Chem. 1995, 99, 9747.
(21) Koch, W.; Frenking, G.; Gauss, J.; Cremer, D.; Collins, J. R. J.
Am. Chem. Soc. 1987, 109, 5917.
(22) Rauhut, G.; Pulay, P. J. Phys. Chem. 1995, 99, 3093.

11156 J. Am. Chem. Soc., Vol. 122, No. 45, 2000

Rozas et al.

Figure 1. Structures of minimum energy found for the ylides calculated at the MP2/6-311++G** level. Distances in angstroms.
Table 1. Protonation Energy (Eprot, kcal/mol) of the Protonated
Ylides Calculated at the MP2/6-311++G** Level, Calculated
Including the B3LYP/6-31G* Zero-Point Scaled Vibrational
Correction (Ref 22)
X-Y + H+ f [X-YH]+

Eprot

H2O-NH + H+ f [H2O-NH2]+
H2O-O + H+ f [H2O-OH]+
H3N-NH + H+ f [H3N-NH2]+
H3N-CH2 + H+ f [H3N-CH3]+

236
209
251
280

Me2O-NH + H+ f [Me2O-NH2]+
Me2O-O + H+ f [Me2O-OH]+
Me3N-NH + H+ f [Me3N-NH2]+
Me3N-CH2 + H+ f [Me3N-CH3]+

248
222
262
288

species, Eprot ) 11 kcal/mol for [Z3N-NH3]+ species, Eprot

) 12 kcal/mol for [Z2O-NH3]+ species, and Eprot) 13 kcal/
mol for [Z2O-OH2]+ species).
Hydrogen-bonded complexes can be considered as intermediates in the protonation process. Thus, the gas-phase basicity of
a molecule (that is, its stability as a protonated species) could
indicate the ability of that molecule to behave as a HB acceptor.
Thus, the ylides studied here, in principle, show a very high
tendency to form strong HB complexes (very high HB basicity).
Hydrogen-Bonded Complexes: Geometry and Energy.
The complexes formed by the non-methylated and methylated
ylides and the three HB donors previously mentioned (HF, HCN,
and HCCH) were computed at the three levels of theory, and
the optimized geometries at the highest level (MP2/6-311++G**)
are gathered in Figures 2 and 3, respectively. The MP2/6311++G** total energy, the B3LYP/6-31G* ZPE scaled
vibrational correction, and the zero-point corrected energies (au)
for the dimers are gathered as Supporting Information.

Figure 2. Structures of minimum energy found for the HB complexes

with the demethylated ylides calculated at the MP2/6-311++G** level.
Distances in angstroms, angles in degrees.

Ylides with N, O, and C Atoms as H Bond Acceptors

J. Am. Chem. Soc., Vol. 122, No. 45, 2000 11157

Figure 3. Structures of minimum energy found for the HB complexes with the methylated ylides calculated at the MP2/6-311++G** level.
Distances in angstroms, angles in degrees.

In the case of complexes between the non-methylated ylides

and HF, a spontaneous double proton transfer between the ylides
and the HF occurs. Thus, the HF donates the proton to the end of the ylide molecule, and this molecule donates a H atom
from its + end to the F- anion. As a result, it was impossible
to obtain, at any level of theory, any HB complex of an ylide
with HF as a donor since the spontaneous double proton transfer
took place in all cases. Similarly, a single proton transfer also
occurred in the case of the Me3N-CH2 ylide with both HF and
HCN donors. In a previous paper we had observed this kind of
spontaneous double proton transfer between amine oxides and
HF.3
As observed in Figure 2, in the case of the non-methylated
ylides, the stationary points found showed several interactions
between HB donors and acceptors. These interactions were
established not only through the more negatively charged ylide
atom, but also by means of the H atoms bonded to the most
positively charged ylide atom. Thus, both molecules in the
complex were simultaneously acting as HB donors and acceptors, providing cyclic complexes in all cases, except for the
H2OsOHCN case, where only one possible HB interaction
was established. In the complexes with HCCH, a HB interaction
with the -cloud of this molecule was observed.23
In the case of the complexes formed by the methylated ylides,
only one interaction was established with the HB donors, as
can be observed in Figure 3, because the H atoms bonded to
the positively charged ylide atom were substituted by CH3
groups.
The distances obtained (between the H atom of the HB donor
and the most negatively charged atom of the ylide; see Figures

2 and 3) were in agreement with HB interactions, except for

the case of the H2OOHCN complex (2.70 ), in which the
angle around this H atom (<90) confirms that no HB can be
established.
Regarding the interaction energies, we report only those
results obtained with the largest basis sets (B3LYP/6-311++G**
and MP2/6-311++G**), which are shown in Table 2. In this
table, both the interaction energy and that corrected by the BSSE
effect for all the complexes studied are gathered.
It is known that the BSSE effect is larger for the MP2
calculations than for the B3LYP ones when a TZP basis set is
used.23,24 However, since all the interaction energies are, in
general, quite large, corresponding to strong interactions (as
expected from this kind of low-barrier HBs), the BSSE effect
will not introduce significant qualitative variations as occurs
for the case of weak interactions.
AIM Analysis of the Ylides and Their Hydrogen-Bonded
Complexes: Atomic Charge, Electron, and Energy Density.
The results obtained for the electron density (FBCP), its Laplacian
(2FBCP), and the energy density (HBCP) at the bond critical
points (BCPs) are evaluated by means of the AIM approach at
the MP2/6-311++G** level for the isolated ylides and their
HB complexes. These are shown in Tables 3 and 4.
The characteristics and changes that occur in the electronic
nature of the bond between the two charged heavy atoms in
the ylide molecules have been analyzed. The results of the
electron density analysis of these ylide bonds, in the isolated
molecules and within the HB complexes, are gathered in Table
3. In all the cases the FBCP of the ylide bond is larger when this
molecule is included in a HB complex, as if the formation of a

(23) Rozas, I.; Alkorta, I.; Elguero, J. J. Phys. Chem. A 1997, 101, 9457.

(24) Alkorta, I.; Rozas, I.; Elguero, J. J. Phys. Chem. A 1998, 102, 9278.

11158 J. Am. Chem. Soc., Vol. 122, No. 45, 2000

Rozas et al.

Table 2. Interaction Energies without (EI, kcal/mol) and with the BSSE Correction (EI+BSSE, kcal/mol) for All the HB Complexes Studied
B3LYP/6-31G*
H2O-NH
H2O-O
H3N-NH

Me2O-NH
Me2O-O
Me3N-NH
Me3N-CH2

X-Y

H2O-O
H3N-NH

Me2O-NH

Me2O-O

Me3N-NH

Me3N-CH2

MP2/6-311++G**

EI

EI+BSSE

EI

EI+BSSE

EI

EI+BSSE

HF
HCN
HCCH
HF
HCN
HCCH
HF
HCN
HCCH

-14.5
-12.4
-13.3
-12.7
-17.1
-10.8

-10.8
-8.6
-9.4
-8.8
-13.5
-8.1

-10.2
-7.3
-12.1
-8.1
-12.4
-8.0

-9.1
-6.7
-11.4
-7.6
-11.4
-7.3

-11.0
-8.5
-12.8
-9.5
-13.4
-9.7

-8.6
-6.4
-10.1
-7.1
-10.4
-7.2

HF
HCN
HCCH
HF
HCN
HCCH
HF
HCN
HCCH
HF
HCN
HCCH

-32.1
-14.0
-10.1
-30.7
-13.0
-10.4
-33.7
-15.3
-9.4
-10.1

-23.2
-11.6
-7.4
-21.4
-9.8
-6.9
-23.5
-12.4
-6.4
-7.2

-21.5
-9.9
-5.3
-18.4
-8.5
-4.6
-26.8
-12.2
-6.4
-6.3

-20.0
-9.3
-4.7
-17.5
-8.2
-4.4
-25.3
-11.7
-5.9
-5.9

-21.2
-11.1
-7.1
-18.8
-9.5
-6.4
-24.6
-13.1
-8.3
-8.2

-16.9
-9.1
-5.3
-15.1
-7.9
-4.7
-20.2
-11.1
-6.1
-6.2

Table 3. Electron Density (FBCP, e/au3), Laplacian (2FBCP, e/au5),

and Energy Density (HBCP, hartrees/au3) Calculated at the Bond
Critical Points of the Ylides, Isolated and within the HB
Complexes, at the MP2/6-311++G** Level
H2O-NH

B3LYP/6-311++G**

H-Z

FBCP(X-Y)

2FBCP(X-Y)

HBCP(X-Y)

isolated
HCN
HCCH
isolated
HCN
HCCH
isolated
HCN
HCCH

0.161
0.176
0.175
0.222
0.244
0.232
0.269
0.276
0.273

0.206
0.165
0.164
0.318
0.250
0.280
-0.253
-0.294
-0.280

-0.089
-0.108
-0.106
-0.128
-0.155
-0.141
-0.236
-0.244
-0.241

isolated
HF
HCN
HCCH
isolated
HF
HCN
HCCH
isolated
HF
HCN
HCCH
isolated
HCCH

0.202
0.221
0.213
0.207
0.260
0.269
0.265
0.262
0.288
0.287
0.290
0.287
0.203
0.203

0.094
0.009
0.048
0.069
0.229
0.177
0.202
0.216
-0.324
-0.349
-0.345
-0.327
-0.244
-0.250

-0.139
-0.166
-0.155
-0.147
-0.177
-0.186
-0.183
-0.178
-0.259
-0.252
-0.259
-0.256
-0.243
-0.242

HB would enforce this particular bond. In addition, this ylide

bond becomes slightly shorter (see Figures 1-3), in agreement
with the relationships found between the electron density and
the bond distance.25 In general, the increment in density is larger
for the non-methylated ylides (FBCP 0.004-0.022), forming
standard HB or double interaction complexes, than for the
methylated ones (FBCP 0.002-0.019), in which only
standard HB complexes can be formed. Between these methylated ylide complexes, there are some exceptions. For example,
in the complex of Me3N-NH with HF and with HCCH and in
the complex of Me3N-CH2 with HCCH, the FBCP is slightly
(25) (a) Alkorta, I.; Barrios, L.; Rozas, I.; Elguero, J. Theochem 2000,
496, 131. (b) Espinosa, E.; Souhassou, M.; Lachekar, H.; Lecomte, C. Acta
Crystallogr. 1999, B55, 563. (c) Alkorta, I.; Rozas, I.; Elguero, J. Struct.
Chem. 1998, 9, 243. (d) Pendas, A. M.; Costales, A.; Luana, V. J. Phys.
Chem. B 1998, 102, 6937.

smaller than or equal to that of the corresponding isolated ylide

(FBCP values of -0.001, -0.001, and 0.000, respectively).
Regarding the nature of these ylide bonds, according to the
results obtained for the energy density at the BCP (Table 3),
they can be considered as covalent bonds in the isolated
molecules, in agreement with the results obtained by Molina et
al. for the X2OO derivatives and related structures,9 as well as
within the HB complexes (HBCP < 0, always). The sensibility
of the HBCP parameter, which provides all negative values,
reflects the covalent nature of these bonds compared with the
2FBCP, which shows some positive values that could erroneously lead to the conclusion that some of the bonds were
closed-shell interactions. These kinds of exceptions in the
behavior of the Laplacian have been already pointed out.26
The electron density analysis of the HB interactions established in these ylide complexes is collected in Table 4. For the
non-methylated ylides, only those complexes formed between
H2ONH and H3NNH with HCN show a unique interaction
between the negatively charged atom (N in both cases) and the
HB donor. In the case of the H2ONHHCN complex, this
interaction can be considered as a HB, taking into account the
electron density value (10-2 au), the positive values of the
Laplacian and the energy density, and the NH distance
(smaller than the sum of the van der Waals radius). However,
in the H3NNHHCN complex, the electron density is rather
large, its Laplacian is positive, the HBCP is negative, and the
NH distance is small. This all indicates the formation of a
very strong HB or a LBHB with the ylide.
In the rest of the complexes, the same HB interaction between
the negatively charged atom of the ylide molecule and the
corresponding HB donor is established (see Table 4). However,
a second interaction occurs in which the ylide acts as a HB
donor (through the H bonded to the positively charged atom),
whereas HCN and HCCH act as HB acceptors (through the N
atom of the HCN molecule or through the triple bond of the
HCCH molecule; see Figure 2). These secondary interactions
should also be considered as HB interactions upon looking at
the density values, the positive sign of Laplacians and energy
densities, and the corresponding distances (see Table 4). An
(26) Gonzalez, L.; Mo, O.; Yanez, M.; Elguero, J. J. Chem. Phys. 1998,
109, 2685.

Ylides with N, O, and C Atoms as H Bond Acceptors

J. Am. Chem. Soc., Vol. 122, No. 45, 2000 11159

Table 4. Electron Density (FBCP, e/au3), Laplacian (2FBCP, e/au5), and Energy Density (HBCP, hartrees/au3) at the Bond Critical Point of the
HB Interactions within the Complexes Calculated at the MP2/6-311++G** Level
X-Y
H2O-NH
H2O-O
H3N-NH
Me2O-NH
Me2O-O
Me3N-NH
Me3N-CH2
a

H-Z

FBCP(YH)

2FBCP(YH)

HBCP(YH)

d(YH)a

HCN
HCCH
HCN
HCCH
HCN
HCCH
HF
HCN
HCCH
HF
HCN
HCCH
HF
HCN
HCCH
HCCH

0.030
0.013 (OH(CtC), 0.022)
0.020 (OHN, 0.039)
0.014 (OH(CtC), 0.026)
0.052
0.029 (NH(CtC), 0.014)
0.097
0.032
0.021
0.085
0.032
0.021
0.117
0.038
0.025
0.022

0.088
0.038 (0.064)
0.062 (0.108)
0.045 (0.069)
0.104
0.091 (0.053)
0.073
0.086
0.069
0.164
0.101
0.066
-0.001
0.093
0.070
0.046

0.000
0.001 (0.001)
0.000 (-0.004)
0.001 (0.000)
-0.011
0.001 (0.002)
-0.047
-0.001
0.002
-0.031
0.000
0.001
-0.070
-0.003
0.001
0.000

1.950
2.504 (2.116)
2.689 (1.763)
2.424 (2.020)
1.732
1.975 (2.536)
1.464
1.932
2.112
1.460
1.869
2.089
1.395
1.857
2.071
2.255

The HB distances (), at the same level of calculation, are also included.

Table 5. Electron Density (FBCP, e/au3), Laplacian (2FBCP, e/au5),

and Energy Density (HBCP, hartrees/au3) Calculated at the Bond
Critical Points of Some of the HB Donors, within the HB
Complexes, at the MP2/6-311++G** Level
Me2ONH
Me2O-O
Me3N-NH

H-Z-W

FBCP

2FBCP

HBCP

H-F
H-CN
HCtN
H-F
H-CN
HCtN
H-F
H-CN
HCtN

0.259
0.264
0.455
0.284
0.268
0.455
0.230
0.257
0.455

-1.486
-0.974
-0.305
-1.821
-0.990
-0.301
-1.082
-0.937
-0.312

-0.479
-0.273
-0.816
-0.557
-0.278
-0.816
-0.385
-0.264
-0.815

exception is found for the double-bonded H2OO:::HCN complex, in which the interaction formed between one of the H
atoms of the ylide and the N atom of the hydrogen cyanide
(see Figure 2) shows negative HBCP and a very short HN
distance, implying a very strong HB.
In the methylated ylide series, a unique interaction was found
between the negatively charged atom of the ylide molecules
and the HB donors. In all the complexes formed with HCCH,
the interaction can be described as a standard HB (FBCP 10-2
au, 2FBCP and HBCP positive). However, in all the complexes
formed with HF, the HBCPs of the HB interaction were negative,
the values of the FBCP were very large, and the YH distances
very short (see Table 4), indicating that the HB interaction is
very strong. It could be considered that maybe the proton had
already been transferred and that the protonated ylide was
interacting with the F atom. However, the electron densities,
2FBCP, and HBCP of the corresponding H-F bonds within the
complexes (see Table 5) indicate that those are covalent bonds.
In the complexes with HCN, both situations are found. The
interaction established in the Me2OOHCN complex shows
FBCP around 10-2 au, and positive 2FBCP and HBCP, whereas
in the complexes with Me2ONH and Me3NNH the 2FBCP values
are positive and the HBCP values are negative and very small.
Again, the electron density characteristics of the bonds of the
HCN molecules within the complexes correspond to covalent
bonds (see Table 5). Both situations are illustrated in Figures 4
and 5.
Due to the distinctive nature of ylides, which are neutral
species with two charged atoms, the variation in their atomic
charges when the HB complexes are formed has been studied.
The AIM atomic charges for the heavy atoms of the ylides
(isolated and within the complexes) and those for the HB donors

Figure 4. Contour plot of the electron density of the Me2ONHHCN

complex calculated at the MP2/6-311++G** level.

were computed at the MP2/6-311++G** level of theory and

are shown in Tables 6 and 7, respectively.
For the demethylated ylides within the complexes, the
negatively charged atom, which is involved in the HB interaction, always suffers an increment of atomic charge, whereas
the positively charged atom can increase or decrease the number
of electrons when the different interactions are established.
When the complexes are formed, the total charge transferred is
negative (from the HB donor to the ylide) when double
interactions take place and positive (from the ylide to the HB
donor) when single HB interactions take place. An exception
is the case of the double-bonded H3NNH:::HCCH complex,
when the Q is positive even though two interactions are
established. However, in this case the second interaction
(between the positively charged N atom and the triple bond of
the HCCH molecule) seems to be very weak when looking at
the electron density and HB distance.
For the complexes formed between strong HB donors and
the methylated ylides, which establish single HB interactions,
in general, a decrease in the atomic charge of the interacting
atom (the negatively charged) is observed (see Table 6).

11160 J. Am. Chem. Soc., Vol. 122, No. 45, 2000

Rozas et al.
Table 7. AIM Atomic Charges Calculated for All the Atoms of
the HB Donors, Isolated and within the HB Complexes, at the
MP2/6-311++G** Level of Theory
N(H) N(C)
HCCH isolated
(H2)ON(H)
(H2)OO
(H3)NN(H)
(Me2)ON(H)
(Me2)OO
(Me3)NNH
(Me3)NCH2

HCN

HF
Figure 5. Contour plot of the electron density of the Me2OOHCN
complex calculated at the MP2/6-311++G** level.
Table 6. AIM Atomic Charges Calculated for the Ylide Atoms in
the Isolated Monomers and within the HB Complexes, at the
MP2/6-311++G** Level of Theory
N(X-) N(X-) N(-Y) N(-Y)

X-Y
(H2)O-N(H)

isolated
HCN
HCCH
isolated
HCN
HCCH
isolated
HCN
HCCH

8.928
8.921
8.937
8.776
8.763
8.781
7.668
7.682
7.684

isolated
HF
HCN
HCCH
(Me2)O-O
isolated
HF
HCN
HCCH
(Me3)N-N(H) isolated
HF
HCN
HCCH
(Me3)N-C(H2) isolated
HCCH

8.815
8.782
8.801
8.808
8.665
8.629
8.646
8.653
7.668
7.698
7.679
7.676
7.955
7.958

(H2)O-O
(H3)N-N(H)

(Me2)O-N(H)

-0.007
0.009
-0.013
0.005
0.014
0.016
-0.033
-0.014
-0.007
-0.036
-0.019
-0.012
0.030
0.011
0.008
0.003

7.576
7.598
7.588
8.499
8.528
8.526
7.761
7.767
7.774
7.657
7.639
7.670
7.669
8.547
8.528
8.551
8.552
7.776
7.764
7.789
7.779
6.101
6.092

0.022
0.012
0.029
0.027
0.006
0.013
-0.018
0.013
0.012
-0.019
0.004
0.005
-0.012
0.013
0.003
-0.009

However, there is no uniformity in these results, since the atomic

charge of the ylide atoms varies in each complex without
following a pattern. In contrast, in all these complexes, the total
charge transferred is always positive (from the HB donor to
the ylide) and proportional to the strength of the HB donor.
Thus, Q is between 0.098 and 0.160 for the HF complexes,
between 0.037 and 0.063 for the HCN complexes, and between
0.013 and 0.046 for the HCCH complexes. Moreover, within
each group of a certain HB donor, the Q follows always the
same tendency regarding the acceptors: Me3NNH > Me2ONH
> Me2OO.
Structure-Energy-Electron Density Characteristics Correlations. Some of the complexes studied here show large EI
and FBCP (10-1 au) values, short HB distances, and positive
2FBCPs, but negative and small HBCPs (see Table 4). These

isolated
(H2)ON(H)
(H2)OO
(H3)NN(H)
(Me2)ON(H)
(Me2)OO
(Me3)NNH

isolated
(Me2)ON(H)
(Me2)OO
(Me3)NNH

0.843
0.757
0.754
0.702
0.732
0.741
0.714
0.719

6.157
6.169
6.160
6.201
6.191
6.191
6.198
6.196

N(C) N(H)
6.157
6.215
6.209
6.260
6.237
6.227
6.259
6.269

Qa

0.843
0.833 -0.026
0.828 -0.049
0.854
0.017
0.857
0.017
0.854
0.013
0.862
0.033
0.862
0.046

N(H)

N(C)

N(N)

Qa

0.779
0.674
0.755
0.617
0.666
0.673
0.642

5.231
5.264
5.096
5.333
5.279
5.271
5.298

7.990
8.101
8.130
8.122
8.105
8.093
8.123

0.039
-0.019
0.072
0.050
0.037
0.063

N(H)

N(F)

Qa

0.288
0.317
0.292
0.344

9.712
9.813
9.806
9.816

0.130
0.098
0.160

The total charge transferred is also given.

last three characteristics have been found as well by other

authors (B3LYP/6-31+G**: phosphinic dimer, d(OH) )
1.598, FBCP ) 0.051, 2FBCP ) 0.159, HBCP ) -0.002;
dimethylphosphinic dimer, d(OH) ) 1.555, FBCP ) 0.054,
2FBCP ) 0.167, HBCP ) -0.003).26 Moreover, our results for
the Me3NNHHF complex show large EI and FBCP values and
a short HB distance, but both the Laplacian and the energy
density are negative. We have found that the electron density
characteristics of the strong HB complex [FHF]- (EI
50 kcal/mol27) at the MP2/6-311++G** level are FBCP ) 0.174,
2FBCP ) -0.348, and HBCP ) -0.206. Taken together, one
may reasonably suggest that these criteria may help characterize
HBs. Thus, considering the classification of HBs as weak when
the EI is <12.0 kcal/mol, medium when EI is between 12.0 and
24.0 kcal/mol, and strong when EI is >24.0 kcal/mol,28 we have
found that weak HBs show both 2FBCP and HBCP > 0, and
medium HBs show 2FBCP > 0 and HBCP < 0, while strong
HBs (and therefore LBHBs) show both 2FBCP and HBCP < 0
(see Tables 2 and 4).
Some authors have described a certain relationship between
the EIs of HB complexes and the corresponding proton
affinities.4c,29 We have found that, considering independently
the different HB donors, the trends in the EIs follow that of
the methylated ylides Eprots. That is, there is a direct relationship between the size of the EI of a complex and the Eprot of
the corresponding ylide (Me3NNH > Me2ONH > Me2OO).
Other relationships that have been used widely in the study
of HB complexes (RXHsYP) are those described between
the EIs and the XY or XH distances. However, we have found
that the EI of our complexes correlates better with the XH/XY
ratio. This XH/XY parameter not only represents the distance
between the heavy atoms involved in the HB interaction (XY)
or the distance of the HB interaction itself (XH) but also, by
considering the ratio between both distances, includes a certain
(27) March J. AdVanced Organic Chemistry, 4th ed.; John Wiley &
Sons: New York, 1992.
(28) Alkorta, I.; Rozas, I.; Elguero, J. Chem. Soc. ReV. 1998, 27, 163.
(29) Mayer, P. M. J. Phys. Chem. A 1999, 103, 5905.

Ylides with N, O, and C Atoms as H Bond Acceptors

Figure 6. Calculated interaction energies (EI, kcal/mol) as a function

of the XH/XY ratio of distances calculated for a series of RXHs
YP complexes. Represented by squares, complexes calculated in this
paper at the MP2/6-311++G** level: 1, H2ONHHCN; 2, H3NNHHCN; 3, Me2ONHHCCH; 4, Me3NCH2HCCH; 5, Me3NNH
HCCH; 6, Me2OOHCN; 7, Me2OOHCCH; 8, Me2ONHHF;
9, Me3NNHHF; 10, Me2OOHF; 11, Me2ONHHCN; 12, Me3NNHHCN. Represented by circles, complexes calculated in ref 23
at the MP2/6-31++G** level: 13, HCOO-HOOCH; 14, HCOOHHOOCH; 15, HCOO-HOH; 16, HCOOHHOH; 17,
(H2O)HCOO-HOOCH; 18, (H2O)HCOOHHOOCH; 19, (H2O)HCOO-HOOCH(H2O). Represented by triangles, complexes calculated
in ref 4c at the MP2/6-31+G** level: 20, MeCOOH-OOCMe; 21,
CH2FCOOH-OOCCH2F; 22, CHF2COOH-OOCCHF2; 23, CF3COOH-OOCCF3; 24, FCOOH-OOCF; 25, OHCOOH-OOCOH;
26,CNCOOH-OOCCN;27,HCOOH-OOCF;28,HCOOH-OOCCN;
29,HCOOH-OOCCH2F;30,HCOOH-OOCCHF2;31,HCOOH-OOCCF3;
32, HCOOH-OOCOH.

correction for the possible angle of this interaction since

(XHsY) would not necessarily be 180. To extend this
correlation to the case of LBHBs, we include in our equation
some EIs and distances (calculated at the MP2/6-31+G** level)
from a series of formic acid-formate anion dimers taken from
the literature.4c,30 The linear correlation obtained is represented
in Figure 6, and the corresponding equation,

EI ) -106.001 + 149.589(XH/XY)
r2) 0.94, n ) 32, SD ) 2.37
demonstrates a sufficiently good regression coefficient taking
into account the differences in the systems compared.
Other regressions were tested, such as EI vs d(XH) or EI vs
d(XY). However, their results were worse than that of EI vs
XH/XY. These distance variables have been used by many other
authors to explain the strength of HBs.
Besides, the introduction of a second independent variable
(the XHsY angle) was tested only for the set of complexes
calculated in this paper. Yet, this second variable did not
improve greatly the regression coefficient:

EI ) -98.248 + 138.898(XH/XY)
r ) 0.92, n ) 12, SD ) 1.41
2

EI ) -106.347 + 141.963(XH/XY) + 0.037(XHsY)

r2 ) 0.93, n ) 12, SD ) 1.46
Conclusions
Ylides are very good HB acceptors, forming very stable HB
complexes with quite large EIs, even with weak HB donors

J. Am. Chem. Soc., Vol. 122, No. 45, 2000 11161

such as HCCH (from -4.7 to -7.2 kcal/mol). With strong HB
donors such as HF, when the proton transfer did not take place,
very strong HBs were formed, with EIs between -15.1 and
-20.2 and very short HB distances (between 1.39 and 1.46 ).
This kind of very strong and short HBs is also found in some
of the complexes with HCN.
Taking into account the EIs and Eprots computed and the
total charge transferred when the complexes are formed (Q),
it is possible to order the methylated ylides by their strength as
HB acceptors. Therefore, even though all of them are very good
HB acceptors, Me3NNH seems to be better than Me2ONH,
which is better than Me2OO.
Moreover, we have found that, as the EI of a complex
increases, the Eprot of the corresponding ylide increases.
Therefore, the order of strength within each family of HB donors
was always Me3NNH > Me2ONH > Me2OO.
With respect to the electron density characteristics obtained
for the complexes studied, we suggest that these criteria can be
used to characterize HBs. Thus, we have found that weak HBs
show both 2FBCP and HBCP > 0, and medium HBs show 2FBCP
> 0 and HBCP < 0, while strong HBs (and therefore LBHBs)
show both 2FBCP and HBCP < 0.
Regarding the correlations found, the fact that the XH/XY
ratio correlates better with the EI than the HB distance (XH) or
the distance between heavy atoms (XY) is interesting. It seems
that the HB distance alone does not explain the strength of the
bond because even though XH is very short, the HsY
distance can be elongated, resulting in a weak interaction.
Moreover, the XY distance, in principle, could better reflect
the interaction between HB donor and acceptor. However, since
the XHsY moiety is not necessarily linear, d(XY) could not
be fully representative of the HB interaction. Nevertheless, the
XH/XY ratio expresses the proportion of the HB bond with
respect to the distance between both HB donor and acceptor
systems. This gives a more representative idea of the HB
interaction, and probably for that reason correlates better with
the EI, which reflects the strength of the HB.
By looking at the regression represented in Figure 6, it is
possible to differentiate the normal HBs (upper part of the plot)
from those which are considered LBHBs (lower part of the plot).
Thus, complexes 13, 17, and 19-32 calculated by Pan and
McAllister30 and defined by them as LBHBs appear in the same
area as complexes 8, 9, and 10, which are those formed by Me2ONH, Me3NNH, and Me2OO with HF, in agreement with our
conclusions.

Acknowledgment. The authors thank the Spanish DGICYT

(Project No. SAF 97-0044-C02) for financial support.

Supporting Information Available: Tables of total energy,

B3LYP/6-31G* ZPE scaled vibrational correction, and zeropoint corrected energies for the protonated species, the monomers, and the dimers (PDF). This material is available free of
charge via the Internet at http://pubs.acs.org.

JA0017864
(30) Pan, Y.; McAllister, M. A. J. Am. Chem. Soc. 1997, 119, 7561.