Volume 112, number 2 CHEhlICAL PHYSICS LETTERS 30 November 1964

ELECTRONIC AND STRUCTURAL PROPERTLES OF BORAZINE AND RELATED MOLECULES

Russell J _BOYD, Sai Cheng CHOI and Christopher C. HALE

Depmtttenl of Cl,etttistry, Dalltousie University. Halifax. h’ova Scotia. Canada B3H 453

Keccived 3 September 1984

Ab initio SCF >I0 calculations are reported for benzene, s-triazine, borazinc and boroxine. The Laplacian of the charge
density and the hlullilien population analysis procedure demonstrate that the dclocalization of the ‘ITelectrons decreases
and rhc polariry of the ring bonds increases substantially as the atoms in the ring become more dissimilar. Several other
properties, including distortion of the ring angles. puckering of the ring and nuclear quadrupohu coupling constants, empha-
size the different chemical properties within the isoelectronic series.

I. introduction of the GAUSSIAN 76 program [ 1 l] on the Dalhousie

Borazine, the inorganic analogue of benzene, is
similar UI physical properties and structure but chenti-
ally much more reactive than the prorotype ofaromatic
systems. This is generally attributed [l-3] to the more
localized nature of the TTelectrons in borazine, with
the evidence coming from molecular orbital (MO)
calculations [4-G] and the addition reactions of bora-
zinc vis&vis the clectrophilic substitution reactions
of bcnzcnc. In this work the Laplacian of the charge
density (71 and ab initio h-10 calculations are used to
study the polanty of bonds, the distortion of ring angles
dnd d number of electronic propertiesin the isoelectric
scrles: bewcnc (I), s-triaLine (II), borazinc (III) and
boroxinc (IV).
I II III
2. Methods
The majority of the computations were performed
on a Pcrkin-Elmer 3230 computer using the GAUSSIAN
SO series of programs [S] _The electric field gradients
were evaluated [9.10] by USCof a modified version
University CYBER 170-730 computer. All plots of the
charge density and its Laplacian were obtained by use
of program PLOTDEN [ 1 ‘_I on a Nicolet Zeta 8 plotter
attached to the PE-3230.
3. Results and discussion
A detailed analysis of the comparison between the
theoretical and experimental structures presented in
table 1 is hampered by experimental difficulties [ 14]_
In agreement with previous calculations [15-181 all
molecules excluding benzene are predicted to have
D3,, equilibrium structures_ The 4-31G calculations,
which generally give more accurate geometries than
the minimal STO-3G basis set [ 19,201, predict an
opening of the NCN angle in s-triazine and a closing
of the ring angle at boron in III and IV relative to the
120’ angle of benzene_ These results are in reasonable
agreement with the experimental data except in borox-
IV ine for which little or no ring distortion has been ob-
served. It is also interesting to note that the BN bond
in borazine is substantially longer than the CC bond
in benzene whereas the CN bond of s-triazine is much
shorter; also the BO bond of boroxine is smaller than
the BN bond of borazine. Whereas the bond lengths
within the rings are readily interpreted in terms of the
degree of delocalization and the sizes of the atomic

136 0 009-26 14/84/S 03.00 0 Elsevier Science Publishers B.V.

(North-Holland Physics Publishing Division)
Volumi 112, number 2 CHEhlICAL PHYSICS LETTERS JO November 1984

Table -1
Equilibrium geometriesa)

Molecule Parameter STO-3G 4-316 Experiment b,

benzene r(CC) 1.387 1.384 1.396 + 0.001

(kh) r(CH) 1.083 1.072 1.083 i 0.004

s-triazine r(CN) 1.354 1.328 1.338

(Dsh) WH) 1.091 1.065 (1.084)
UNCN) 126.4 123.6 126.8
L(CNC) 113.6 116.4 113.2

borazine r(BN) 1.418 1.430 1.436 2 0.004

(&h) r(BH) 1.161 1.187 1.258 -c 0.020
r(NH) 1.019 0.994 1.050 i 0.020
L(NBh3 117.2 117.5 117.7 -c 2.0
L(BNB) 122.8 122.5 121.1 i 2.0

borosine r@O) 1.362 1.368 1.376 -c 0.004

cD3$ r(BW 1.162 1.169 1.19 = 0.02
L(OB0) 119.4 115-5 120.0 I 0.7
L(BOB) 120.6 124.5 120.0 i 0.7

a) Bond lengths in sngstrdm and angles in degrees.

b, From ref. 1131.

orbitals, there appears to be no simple explanation for and LNBN = 117.6“. Thus we conclude that adding
the ring angles. As a check on the 431G results, bora- polarization functions to the basis set of the heavy
zine has been optimized at the 6-31G* level [21]: atoms has very little effect on the equilibrium structure_
I = 1.426 a, I = 1.193 a, ~(NII) = 0.996 a The Mull&en charges [22] listed in table 2 indicate

Table 2
4-31G charge distributions and quadrupolar coupling constants

hloleculc Atom hMliicn population Bader QCCa)

total
z
u electrons = electrons total

benzene C 5.189 1.000 6.189 5.996 2.26

H 0.811 0.811 1.002 0.243

s-triazine C 4.886 0.823 5.709 5.062 3.17

N 6.362 1.177 7.538 8.009 5.23
HC 0.753 0.753 0.922 0.244

borazine B 3.822 0.301 4.123 2.869 7.15

N 6.451 1.699 8.150 8.861 1.90
HB 7.077 1.077 1.603 0.161
HN 0.650 0.650 0.634 O-326

borosine B 3.819 0.247 4.065 2.816 7.19

0 7.149 1.753 8.902 9.538 5.87
HB 1.032 1.032 1.659 0.170

al The quadrupolar coupling constants, X = e2qzzQ/h, have been calculated using the following quadrupole moments for r”B
(Q = 8.5 X 10wz6 cm* [23]), “C (Q = 3.1 X 1O’6 cmZ [23]), *H (Q = 2.860 X lo-” cm* [24]), 14N (Q = 1.93 X 1O-26 cm’
[25]) and t’0 <Q = 2.6 X lo-26 cm* 1231). All values are in MHz.

137
Volume 112. number 2 CHEMICAL PHYSICS LETTERS 30 November 1984

taht the polarity of the ring bonds increases with the
dissimilarity of the nuclear charges of the atoms. The
polarization of u electrons in the ring (0.361. 1.101
and I .I 50e in II, 111and IV, respectively) is augmented
by a 0.177 n-electron shift in II and opposed by 0.301
and 0.247 n-electron acceptances by B in III and IV,
respectively. Thus, the very large increase in o-electron
cloud polarity between s-triazine and borazine is par-
tially offset by differences in the x-electron cloud; each
C loses 0.177e to the N atoms whereas the 7reIectron
deficient B atoms of III and IV accept ofelectrons from
the N and 0 atoms. It should be noted that the larger

_.____--.---- ___----__.-
____---- -_--- ~“---_:-T---
___-- --- ’ , . Tr-------
/ ’ ;’ ‘;
-----a
. _________ . _I
__- -- _\q. 1
_ it

Fi;. I. Contour map of the charge density in the molecuix plane: (a) benzene, @) s-triaziue, (c) borazine, (d) boroxine. The
contour values in au are 0.002.0.004 and 0.008 increasing in powers of 10. The outermost contour in each plot is 0.002 au. The
orientation or eachmolecule corresponds to the strucruml formufae given in section 1.

138
Volume 112, number 2 CHEMICAL PHYSICS LETTXRS 30 November 1984

net charge on N in III than on 0 in IV is due to N---H
bond polarity and not to differences within the rings.
More insight into the electronic structure of bora-
zine and related compounds is provided by the charge
density maps shown in fig. I. In the vicinity of each
C-H pair, p(r) in s-triazine remains very similar to
benzene,whiIe the electron cloud around each N atom
shows a much greater concentration of charge. Further
disortion, due to the bonding of a H atom to each N
and the replacement of each C by B, is evident in
borazine. Note that the BH and NH bonds are more
and less polarized, respectively, toward H than the
CH bonds. The plot for boroxine shows very similar
ring polarity to the borazine plot, while the electron

Fig. 2. Countour map of 7$(r) in the molecular plane: (a) benzene, (b) s-triazine, (c) borazine, (d) bornaine. Positive values of
v;(r) are denoted by solid contours, negative vabres by dashed contours. The contour values in ZXIitse -c 0.002, rt 0.004 and
2 0.008 increasing in powers of 10. The orientation of each molecule given in section 1.

139
Volume 112. number 2 CHEMICAL PHYSICS LETTERS 30 November 1984

distribution around the 0 atom is qualitatively similar

to rhe N atoms of s-triazine.
An cvcn more sensitive probe of the electronic struc-
ture of a molecule is provided by the Laplacian of the
charge density, V:(r), which determines the regions
of space wherein the electronic charge of a molecule
IS locally concentrated anddepleted [26] .This function
has been shown to demonstrate the existence of local
concentrations of electronic charge in both the bonded
and non-bonded regions ofan atom III a molecule 17,261,
wItbout recourse to any orbital model or arbitrary rcfer-
cncc state. Interactions resulting from the sharing of
charge density between atoms,,as in covalent and polar
bonds, are characterized by V&) < 0. A large region
between the carbon atoms of benzene in which V:(r)
< 0 (see fog. 2) emphasizes the strong covalent bond.
The corresponding plot for s-tnazine indicates a small
polarization of the covalent CN bond, with the lone -12 -6 lzl 6 12
pairs [7] on the nitrogen atoms clearly visible. The
rig. 3. Onediniensional cross section of tk conformational
substantial polarization of the BN bonds in borazine
energy (in kcai/mole) hypcrsurface for puckering of the six-
and the BO bonds in boroxine is demonstrated by the membered ring in benzene (upper curve) and bora_&w (lower
V:(r) plots. As expected, the oxygen lone pairs in curve).
boroxinc arc less dilTuse than their nitrogen countcr-
parts in s-triazinc. Here it should be emphasized that
non-bonded charge concentrationsare thinner in radial X-ray diffraction [32] and spectroscopic [33]
extent than are the bonded ones [7]. studies on (R6 B,N,)Cr(CO), complexes have shown
Numerical integration of p(r) over regions of space that the borazine ring is puckered with the actual struc-
dcllned by the gradient vector field [27-291 of p(r) ture intermediate between a true TI complex, as ob-
yields the total elcctromc charge associated with each served in C6HsCr(CO),, and a pure u complex in which
atom. With the exception of the CH bonds of benzene the arrangement about the N atoms is nearly tetrahedral.
and s-triazinc. Badcr’s partitioning method [30] leads Fig. 3 compares the potentials of benzene and borazine
to greater polarities than the Mulhken population in which alternate atoms of the ring are displaced
analysts (see table 2). above and below the plane such that the angle of dis-
To further characterize the clcctronic structure of placement is the same for all atoms. The much lower
borazinc and related molecules we have calculated the potential for borazine further demonstrates that the
cleclric field gradients, as described elsewhere [9], for ‘ITelectrons are substantially less delocalized than in
c.rch of the The results are listed in table 2 in
nuclei. benzene. With a displacement of ISo, corresponding
rlcc iorm orquadrupolar couplingconstants,~s,which to the crystal structure [32] in which the two parallel
in Iurn arc important for a full understanding of certain planes formed by the three boron atoms and the three
nucloJr magnetic resonance spectra. From the ratio of nitrogen atoms are separated by 0.07 a, the increase
the Iq’N and “B quadrupolar coupling constants in in energy from the planar structure is only 2.1 kcal/mole
solulion 13 11, the cxperiniental ratio of Lhe clcclric in borazine and 3.4 kcal/mole in benzene. In borazine
licld gradren ts is 0.73, whereas our 4-3 1G calculations complexes this can be provided by the formation of
yield 1.17 for r/lZ(N)/rlZZ(B) In view of the fact that three essentially u bonds LOthe N atoms, whereas a
rbc calculations ignore the effect of the solvent, and x-type interaction is preferred in the arene metal
Iiartrec-Fock quality basis sets arc impractical for carbonyls. Apd finally we note that the relative po-
~nolcculcs as large as bozarine, the agreement is fairly tential for ring puckering in s-triazine is comparable
s3tisfactoIy. to that of benzene, since the shorter bond length
Volume 112, number 2 CHEMICAL PHYSICS LETTERS 30 November I984

largely offsets the effect oflessn delocalization,while [ 111 J.S. Binklcy, R.A. Whiteside, P.C. Hariharan, R. Seeger,
the relative potential for boroxine lies about 18% below J.A. Pople, W.J. Hehre and h1.D. Newton, QCPE 11
(1978) 368.
the borazine curve.
[ 121 R.F.W. Bader. Department of Chemistry. Mchfaster
University, Hamilton, Ontario. Canada L8S 4Ml.
[ 131 J.H. Callomon, E. Hirota, K. Kuchitsu. W-J. Lafferty.
Acknowledgement -4.G. hIaki and C.S. Pote, in: Structure data of free
polyatomic molecules_ Landoit-BZimstein, New Series,
Group II,Vol. 7, cds. K.H. Hellwge and AX. HeIhvege
We would like to acknowledge many helpful dis-
(Springer, Berlin, 1976).
cussions with Professor R.F.W. Bader and the hospi- [ 141 \V_ Harsbbarger, G. Lee. R-F. Porter and S.H. Bauer,
tality extended to one of us (SCC) during visits to Inorg. Chem. 8 (1969) 1683.
McMaster University_ The many comments and [ 151 C.E. Doiron, F. Grrin,T_B. hlchlahon and I;. Vasudevan,
suggestions ofour colleagues, in particular B.A. Pettitt Can. J. Chem. 57 (1979) 1751.
[ 161 H. Kate, K. Hirao and K. Yamashita, J. lIo1. Struct.
and R.E. Wasylishen, and the financial support of the (THEOCHEM) 88 (1982) 265.
Natural Sciences and Engineering Research Council jl7] H. Kate, K. Hirao and hf. Sane, J. Mol. Struct.
of Canada are gratefully acknowledged. (THEOCHEM) 104 (1983) 489.
[ 181 K. Hirao and H. Kato. Chem. Phys. Letters 98 (1983)
340.
[ 191 W-A. Lathan, W-J. Hehre, L.A. Curtiss and J-A. Pople,
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141