CEJC 2(1) 2004 34{51

Aromatic heterocycles XII. Semiempirical PM3

study of Diels-Alder cycloaddition reaction of
substituted phosphabenzenes

Liliana Pacureanu1 ¤ , Mircea Mracec1, Zeno Simon1

Institute of Chemistry of Romanian Academy,
24 Mihai Viteazul Avenue,
300223 Timisoara, Romania

Received 21 July 2003; accepted 2 October 2003

Abstract: We report the results of a semiempirical PM3 study of the 1,4 cycloaddition reaction
of substituted ¶ 3 -phosphabenzenes with alkynes. The in®uence of the nature, position and
steric hindrance of substituents on the reaction energy is studied. Except for some values, the
results are in reasonable agreement with experimental observations and electronic e¬ects of
substituents.
®c Central European Science Journals. All rights reserved.

Keywords: Diels-Alder cycloaddition reaction, ¶ 3 -phosphabenzene, 1-phosphabarrelene, semi-

empirical PM3 method

1 Introduction

Reactivity and coordinating properties of aromatic phosphorus heterocycles di®er from

those of pyridine [1-8]. In the last few years, interest in electronic structure and reactivity
of ¸3 -phosphabenzenes have known increased development [1, 3, 9{11].
¸3 -phosphabenzenes react with nucleophilic reagents and radicals [12]. The Diels-
Alder cycloaddition reaction of ¸3 -phosphabenzenes take place at 1,4 positions giving 1-
phosphabarrelenes without 1,2 cycloaddition to the double bond P=C. The sp2 -hybridized
phosphorus atom confers to ¸3 -phosphabenzenes good ¼-acceptor and poor ¾-donating
properties. In contrast, pyridine is good ¾ donor [1], [3], [7], [8].
Ab initio calculation emphasized no important perturbation of aromaticity due to the
replacement of the CH unit by the phosphorus atom, and the resonance energy of ¸3 -
¤
E-mail: lilypac 99@yahoo.com
L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51 35

phosphabenzene as determined from SCF/3-21G* calculation is 88% of benzene resonance

energy [13]. Nucleus independent chemical shift criteria (NICS) calculated at B3LYP/6-
31G* level showed a value of -10.2 for phosphabenzene, which is close to NICS calculated
for benzene: -11.5 [14].
In phosphabenzene, the more electropositive phosphorus atom bears a positive charge.
The converse situation is that of pyridine where the nitrogen atom is negatively charged.
The lone pair orbital is the HOMO in pyridine where in ¸3 -phosphabenzene the lone
pair is the third occupied level while the LUMO of phosphabenzene is lower in energy
conferring very interesting coordinating properties [10], [15].
The substituted¸3 -phosphabenzenes [16{18] react with highly reactive dienophiles
such as hexa°uorobutyne-2, benzyne, dicyanoacetilene at positions 1,4 to form 1-phos-
phabarrelenes [19{22]. Even the ¾-complexes of 2-pheny-4,5-dimethyl-¸3 -phosphabenzene
with tungsten pentacarbonyl undergo 1,4 cycloaddition reaction [22].
The 1,4 Diels-Alder cycloaddition reaction of ¸3 -phosphabenzenes occurs easily if the
diene character of phosphabenzene is well pronounced. The stabilizing factor for normal
Diels-Alder reactions is the interaction HOMO diene - LUMO dienophile, thus the electron
withdrawing substituents of the dienophile and the electron releasing substituents of the
diene will increase the reaction rate [23].
MÄarkl and Lieb observed the in°uence of the nature of the substituent group on the
1,4 cycloaddition reaction of ¸3 -phosphabenzenes with hexa°uorobutyne-2 (Figure 1)
[21]. The cycloaddition reaction occurs more readily with 2,6-ditertbuthyl-4-methyl ¸3 -

3
Fig. 1 The reaction of ¶ -phosphabenzenes with alkynes.

phosphabenzene and 2,6-dimethyl-4-phenyl-¸3 -phosphabenzene than electron poor 2,4,6-

triphenyl-¸3 {phosphabenzene (Table 4).
MÄarkl, Lieb and Martin [24] obtained benzophosphabarrelenes starting from 2,4,6-
triphenyl and 2,4,6-tritertbuthyl ¸3 -phosphabenzene and arynes. Better yield was ob-
tained with the more electron rich 2,4,6-tritertbuthyl ¸3 {phosphabenzene (Table 4). The
reactions are depicted in Figure 2.
1-Phosphabarrelenes are highly stable, and do not undergo scission or retro Diels-
Alder reaction with split o® alkynes in thermal or ionization conditions [22].
This study was undertaken to ¯nd out the in°uence of the position, nature and steric
hindrance of the substituents of the ¸3 -phosphabenzene on the 1, 4 Diels-Alder cycload-
dition reaction using the semiempirical PM3 method.
36 L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51

3
Fig. 2 The reaction of ¶ -phosphabenzenes with benzyne.

The 1,4-Diels-Alder cycloaddition reaction of phosphabenzene with hexa°uorobutyne-

2 is thermodynamically controlled as M. Mracec et al [9] have shown, in concordance with
Woodward-Ho®man rules [25], [26]. The number of ¼ electrons involved in the reaction
and symmetry predictions prevail, thus the reaction is thermally allowed [25], [26].

2 Method
Molecular geometry calculation and full optimization of reagent and product molecules
were performed with the Hyper-Chem 5.11 program [27]. First we proceed to optimize
all molecules by molecular modeling using force ¯eld MM+. The re-optimization of all
molecules was carried out with semiempirical approximation PM3-RHF for the F operator
[28]. The method of accelerate convergence with a convergence limit of 10¡5 SCF was
chosen. The molecules were considered in vacuum and the optimization algorithm Polack-
Ribiere conjugated gradient with 0,01Kcal/ºAmol RMS gradient was used.

3 Results and discussion

The data resulted from PM3 calculations are shown in Table 3, Table 4 and Table 5.
Special attention was paid to the charges of the centers of reactions: the carbon atom at
position 4 and the phosphorus atom in order to establish the stronger [1], [4] dipole; this
is more important in the case of polarisable dienophiles.
From Table 3 we observed that the alkyl substituents decrease the energy of re-
action. The lowest values of reaction energies were obtained for 2,6 dialkyl substituted
¸3 -phosphabenzenes with a group at position 4 without steric hindrance. On the contrary
electron withdrawing groups at position 2,6 of ¸3 {phosphabenzenes, and a group produc-
ing steric hindrance at position 4 will increase the reaction energy. Alkyl substituents
at position 4 of the 2,6-phenyl ¸3 {phosphabenzenes in°uence the reaction energy. Thus,
methyl and ethyl substituents decrease the reaction energy, while isopropyl and tert-butyl
groups increase the reaction energy. The phenyl electron withdrawing group increases the
heat of reaction with respect to methyl and ethyl groups (Figure 3).
L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51 37

The lowest reaction energy of 2,4,6-trimethyl phosphabenzene is due to minimal steric

hindrance. Electron withdrawing groups phenyl, isopropyl and tertbutyl at position 4
increase the reaction energy. We have no explanation for the higher value of the 4-ethyl
derivative (Figure 4).
Tert-butyl substituents at position 2,6 decrease the reaction energy, especially if po-
sition 4 bears a stronger electron releasing group, without steric hindrance. Phenyl sub-
stituents do not in°uence the reaction energy as much as tert-butyl groups do (Figure 5).
The computed values of reaction energy of 2,4,6-trimethyl-¸3 -phosphabenzene, 2,4,6-
triethyl-¸3 -phosphabenzene and 2,4,6-triisopropyl-¸3 - phosphabenzene are lower than those
of 2,4,6-tritolyl and 2,4,6-tribenzyl-¸3 -phosphabenzene, which is in agreement with the
electronic e®ects of substituents. In the case of phosphabenzene, the absence of steric
hindrance decreases the reaction energy.
In agreement with experimental data the reaction energy of 2,6-ditertbutyl-4-methyl-
¸ {phosphabenzene is lower than the reaction energy of 2,4,6-triphenyl-¸3 -phosphabenzene
3

and 2,6-dimethyl-4-phenyl-¸3 {phosphabenzene.

The data listed in Table 4 shows that alkyl substituents, except ethyl derivatives,
decrease the reaction energy of phosphabenzenes with benzyne. The lower values are
obtained in the case of reaction of 2,6-ditertbutyl-¸3 {phosphabenzenes which bear methyl
and isopropyl substituents at position 4. Tertbutyl and phenyl group at position 4 increase
the reaction energy (Figure 6).
In the case of 2,6-diphenyl-phosphabenzenes, the electron releasing groups methyl,
ethyl, and isopropyl decrease the reaction energy in comparison with 2,4,6-triphenylphos-
phabenzene. A tertbutyl group at position 4 also increase the reaction energy (Figure 7).
The reaction energy in the case of 2,6-dimethyl substituted phosphabenzenes is in-
creased by tertbutyl and phenyl substituents at position 4, but again the heat of reaction
of ethyl derivatives is a little higher than those of methyl derivatives (Figure 8).
The high thermodynamic stability of benzophosphabarrelenes observed experimen-
tally is in agreement with the heat of formation obtained by PM3 calculation. The
reaction energies of phosphabenzenes substituted with methyl groups at position 2,6 are
lower than those of phosphabenzenes substituted with phenyl groups at the same position
but higher than those of tert-butyl substituted phosphabenzenes. 2,4,6-Triethylphospha-
benzene and 2,6methyl-4-ethyl-¸3 -phosphabenzene presents inexplicable higher values for
the reaction energy.
2,4,6-Triisopropyl-¸3 -phosphabenzene presents lower reaction energy while 2,4,6-tri-
tolyl and 2,4,6-tribenzyl-¸3 {phosphabenzenes have higher values of the reaction energy in
agreement with electronic e®ects of substituents. The reaction energy of 2,4,6-tritertbutyl-
¸3 -phosphabenzene is lower than the reaction energy of 2,4,6-triphenyl-¸3 -phosphabenzene
as experimental data shows. In consequence the results of PM3 calculation, except some
values for ethyl derivatives, are in agreement with the experimental data and the elec-
tronic e®ects of substituents.
Atomic charges listed in Table 5 emphasized that the electron withdrawing group
phenyl decreases the atomic charge at C4, while electron releasing groups methyl, ethyl,
38 L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51

isopropyl, and tert-butyl increase the atomic charge at C4, thus the [1], [4] dipole is
strengthen by alkyl groups and consequently the reactions energy of these compounds
are lower. The positive charge of the phosphorus atom increases in the case of phenyl
substituted phosphabenzenes in position 2,4 and 6. The obtained values for phosphorus
charges of 0.471 and for carbon at position 4 of -0.148 are reasonable in comparison
with those obtained with MP2/6-31G* method of 0.55 for phosphorus and -0.25 for C4,
respectively [13].
The energy of the HOMO obtained by PM3 calculation is -9.073eV for ¸3 {phosphaben-
zene and -8.64eV for 2,4,6-tritertbutyl-¸3 {phosphabenzene. The absolute values are close
to the values of ¼ ionization energies of the HOMO orbital given by photoelectron spectra
of phosphabenzene of 9.12 eV [10] and 8.6eV for 2,4,6-tritertbutyl-¸3 {phosphabenzene
[15].

4 Conclusion
The results obtained by PM3 calculation, except for some values, are in good agreement
with the available experimental data. Alkyl substituents decrease reaction energies, but
steric hindrance in°uences the reaction energy, especially if bulky substituents such as
tert-butyl and isopropyl groups are situated at position 4. Electron withdrawing groups
such as phenyl and benzyl increase reaction energies, particularly at position 4. The values
of heat of formation of 1-phosphabenzobarrelenes con¯rm the highly thermodynamic
stability of these compounds.
Atomic charges and HOMO energies resulting from PM3 calculation show reasonable
values compared with those obtained by ab initio calculation and with ionization energies
obtained from photoelectron spectra.

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[24] G. MÄarkl, F. Lieb and C. Martin: \Substituierte benzo-phosphabarrelenes zur
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[26] R. Ho®mann, R.B. Woodward: \Selection rules for concerted cycloaddition reaction"
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L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51 41

Compound R2=R6 R4 Yield [%]

3a C6 H5 C 6 H5 53
3b C(CH3 )3 CH3 89
3c CH3 C 6 H5 41
a: R2=R4=R6=C 6 H5
b: R2=R6=C(CH 3 )3 ; R4=CH3
c: R2=R6=CH3 ; R4= C6 H5 .

3
Table 1 The yields of 1,4 cycloaddition reaction of ¶ -phosphabenzenes with hexa®uorobutyne-2
[21].
42 L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51

Compound R2 =R4 =R6 R Yield [%]

6a C 6 H5 H 15
6b C 6 H5 Cl 17
6c C(CH3 )3 H 69
6d C(CH3 )3 Cl 67
a: R2 =R4 =R6 =C6 H5 R=H
b: R2 =R4 =R6 =C6 H5 R=Cl
c: R2 =R4 =R6 =C(CH3 )3 R=H
d: R2 =R4 =R6 =C(CH3 )3 R=Cl.

3
Table 2 The yields of 1, 4 cycloaddition reaction of ¶ -phosphabenzenes with arynes [24].
L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51 43

No Phosphabenzene ¢Hf ¢Hf ¢H*R

(kcal/mol) (kcal/mol) (kcal/mol)
barrelene
1 2,4,6-triphenyl-phosphabenzene 127.910 -145.820 -19.949
2 2,6-diphenyl-4methyl-phosphabenzene 94.365 -181.469 -22.053
3 2,6-diphenyl-4ethyl-phosphabenzene 89.715 -186.612 -22.546
4 2,6-diphenyl -4isopropyl-phosphabenzene 85.108 -184.389 -15.716
5 2,6-diphenyl-4tbutyl-phosphabenzene 80.652 -186.438 -13.309
6 2,6-diphenyl-4benzyl-phosphabenzene 122.935 -148.733 -17.887
7 2,4,6-trimethyl-posphabenzene 24.291 -254.678 -25.188
8 2,6-dimethyl-4ethyl-phosphabenzene 18.011 -257.208 -21.438
9 2,6-dimethyl-4isopropyl-phosphabenzene 15.110 -261.544 -22.873
10 2,6-dimethyl-4tbutyl-phosphabenzene 9.067 -257.530 -12.816
11 2,6-dimethyl-4phenyl-phosphabenzene 56.107 -216.992 -19.318
12 2,4,6-tritbutyl-phosphabenzene -8.071 -277.422 -15.570
13 2,6-ditbutyl-4methyl-phosphabenzene 5.969 -274.533 -26.721
14 2,6-dibutyl-4ethyl-phosphabenzene -3.331 -277.684 -20.572
15 2,6-ditbutyl-4isopropyl-phosphabenzene -3.429 -281.455 -24.245
16 2,6-ditbutyl-4phenyl-phosphabenzene 39.204 -236.829 -22.252
17 2,4,6-triethyl-phosphabenzene 10.332 -265.176 -21.727
18 2,4,6-triisopropyl-phosphabenzene 9.492 -272.643 -28.354
19 2,4,6-tribenzyl-phosphabenzenez 110.025 -138.175 5.581
20 2,4,6-tritolyl-phosphabenzene 99.419 -174.380 -20.018
21 phosphabenzene 43.050 -240.115 -29.384
*¢Hf of hexa°uorobutyne-2 is -253.781 kcal/mol

Table 3 The heats of formation for reagents, products and reaction energies for the reaction of
substituted ¶ 3 -phosphabenzenes with hexa®uorobutyne-2 as resulted from PM3 calculation.
44 L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51

No Phosphabenzene ¢Ho f ¢Hof ¢HR

(kcal/mol) (kcal/mol) (kcal/mol)
barrelene
1 2,4,6-triphenyl-phosphabenzene 127.910 164.559 -93.099
2 2,6-phenyl-4methyl-phosphabenzene 94.365 128.023 -96.090
3 2,6-pheny-l4ethyl-phosphabenzene 89.715 124.145 -95.318
4 2,6-phenyl -4isopropyl-phosphabenzene 85.108 120.388 -94.468
5 2,6-phenyl-4tbutyl-phosphabenzene 80.652 117.466 -92.934
6 2,6-phenyl-4benzyl-phosphabenzene 122.935 158.364 -94.319
7 2,4,6-trimethyl-phosphabenzene 24.291 57.384 -96.655
8 2,6-methyl-4ethyl-phosphabenzene 18.011 53.520 -94.239
9 2,6-methyl-4isopropyl-phosphabenzene 15.110 49.775 -95.083
10 2,6-methyl-tbutyl-phosphabenzene 9.067 46.927 -91.888
11 2,6-methyl-4phenyl-phosphabenzene 56.107 93.900 -91.955
12 2,4,6-tritbutyl-phosphabenzene -8.071 26.902 -94.775
13 2,6-tbutyl-4methyl-phosphabenzene 5.969 37.613 -98.104
14 2,6-tbutyl-4ethyl-phosphabenzene -3.331 33.731 -92.686
15 2,6-tbutyl-4isopropyl-phosphabenzene -3.429 29.794 -96.525
16 2,6-tbutyl-4phenyl-phosphabenzene 39.204 73.875 -95.077
17 2,4,6-triethyl-phosphabenzene 10.332 45.650 -94.430
18 2,4,6-triisopropyl-posphabenzene 9.492 35.853 -103.387
19 2,4,6-tribenzyl-phosphabenzene 110.025 146.210 -93.563
20 2,4,6-tritolyl-phosphabenzene 99.419 136.268 -92.899
21 phosphabenzene 43.050 75.106 -97.724
*¢Hf of benzyne is 129.748 kcal/mol

Table 4 PM3 calculation of the heat of formation for reagents, products and reaction energies
for substituted ¶ 3 -phosphabenzenes with benzyne.
L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51 45

No Phosphabenzene Atomic Atomic HOMO LUMO

charge charge [eV] [eV]
at P at C4
1 2,4,6-triphenyl-phosphabenzene 0.465 -0.042 -8.355 -1.341
2 2,6-phenyl-4methyl-phosphabenzene 0.444 -0.091 -8.441 -1.160
3 2,6-phenyl-4ethyl-phosphabenzene 0.450 -0.096 -8.467 -1.161
4 2,6-phenyl -4isopropyl-phosphabenzene 0.452 -0.093 -8.473 -1.152
5 2,6-phenyl-4tbutyl-phosphabenzene 0.448 -0.082 -8.455 -1.133
6 2,6-phenyl-4benzyl-phosphabenzene 0.455 -0.093 -8.478 -1.174
7 2,4,6-trimethyl-posphabenzene 0.422 -0.095 -8.589 -0.825
8 2,6-methyl-4ethyl-phosphabenzene 0.433 -0.097 -8.675 0.078
9 2,6-dimethyl-4isopropyl-phosphabenzene 0.432 -0.094 -8.670 -0.776
10 2,6-dimethyl-4tbutyl-phosphabenzene 0.430 -0.083 -8.659 -0.755
11 2,6-dimethyl-4phenyl-phosphabenzene 0.449 -0.046 -8.448 -1.065
12 2,4,6-tritbutyl-phosphabenzene 0.423 -0.082 -8.647 -0.765
13 2,6-ditbutyl-4methyl-phosphabenzene 0.417 -0.095 -8.607 -0.792
14 2,6-ditbutyl-4ethyl-phosphabenzene 0.423 -0.100 -8.654 -0.795
15 2,6-ditbutyl-4isopropyl-phosphabenzene 0.424 -0.096 -8.665 -0.789
16 2,6-ditbutyl-4phenyl-phosphabenzene 0.441 -0.044 -8.428 -1.068
17 2,4,6-triethyl-phosphabenzene 0.433 -0.101 -8.704 -0.798
18 2,4,6-triisopropyl-posphabenzene 0.450 -0.096 -8.467 -1.161
19 2,4,6-tribenzyl-phosphabenzene 0.437 -0.091 -8.772 -0.881
20 2,4,6-tritolyl-phosphabenzene 0.452 -0.038 -8.230 -1.286
21 phosphabenzene 0.471 -0.148 -9.073 -0.793

Table 5 The PM3 calculation for atomic charges, and HOMO and LUMO energy of trisubsti-
tuted -¶ 3 -phosphabenzenes.
46 L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51

3
Fig. 3 Reaction energy as function of substituent at position 4 of 2,6-diphenyl-¶ {
phosphabenzenes.
L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51 47

3
Fig. 4 Reaction energy as function of substituent at position 4 of 2,6-dimethyl-¶ {
phosphabenzenes.
48 L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51

3
Fig. 5 Reaction energy as function of substituent at position 4 of 2,6-ditetrtbuthyl-¶ {
phosphabenzenes.
L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51 49

3
Fig. 6 Reaction energy as function of substituent at position 4 of 2,6-ditertbutyl-¶ {
phosphabenzenes.
50 L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51

3
Fig. 7 Reaction energy as function of substituent at position 4 of 2,6-diphenyl-¶ {
phosphabenzenes.
L. Pacureanu et al. / Central European Journal of Chemistry 2(1) 2004 34{51 51

3
Fig. 8 Reaction energy as function of substituent at position 4 of 2,6-dimethyl-¶ -
phosphabenzenes.