Journal ofMolecular Structure, 50 (19’78) 127-132

OElsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

GEOMETRY OPTIMISED AB INITIO CALCULATIONS ON

CYCLOPROPENONE AND DIMETHYLCYCLOPROPENONE ADDUCTS
WITH BORANE AND TR~~LUOROBOR~E

N. 3. FITZPATRICK and M. 0. FANNING

Department of Chemishy. University Coliege. Betfield. Dublin 4 (Ireland)
(Received 3 March 1978)

ABSTRACT

Geometry optimised ab initio calculations are reported for R,C,O.BY, (R = H, CH,;

Y = H, F). The results show that in the above seriesBH, is a stronger Lewis acid than
BF, and that dimethylation increases the basicity of the cyclopropenone system.

Geometry optimised ab initio calculations are reported for the adducts

cyclopropenone borane (l), d~ethylcyclopropenone - borane (Z), cyclo-
l

propenone. trifluoroborane (3) and dimethylcyclopropenone - trifluoroborane

(4). In the calculations STO-3G [l] basis sets and the Gaussian-70 computer
program of Pople and co-workers were used [Z] . Previously geometry
optimised c.alculationson a range of substituted cyclopropenones [3,4] and
on trifluoroborane [5] have been reported using the STO-3G basis and the
Gaussian-70 program. Also Perkins and co-workers [6] have studied the
electronic structures of some adducts with BF+
The adducts considered in the present work have not been experimentally
reported. However diphenylcyclopropenone forms complexes with a range
of Lewis acids including BF3, SbCIS and substituted acetic acids [ ‘7,8] where
in the t~~uorobor~e complex the G-B bond was presumed to be an electron
pair (a) bond. Hopkins and co-workers have determined the 1 :l equilibrium
constants of a range of substituted cyclopropenones with phenol and corre-
lated their results with CNDO/Z calculations [S] . These authors provide
definitive experimental data on the effects of substituents on the apparent
basicities of cyclopropenones. Breslow and co-workers have considered the
basicities of dialkylcyclopropenones [ 10,111 and in a review Potts and
Baum concluded that di~kylcy~lopropenones are the most basic of a range
of disubstituted cyclopropenones [ 123. Finally an ab initio study of a cyclo-
propenone-water adduct using the Gaussian-70 program has been reported [ 131.
128

Optimised geometries

In Table 1 the optimised geometries are given, which show some general
trends. The B-O bond lengths are large, particularly when Y = F thus
suggesting the instability of the adducts. Experimentally B-O bond lengths
are in the approximate range 1.40 to 1.48 A and a hypothetical B-0 single
bond length is 1.43 A [ 141. However when cyclopropenone is dimethylated
the B-O bond lengths decrease, thus the greater b&city of the alkylated
cyclopropenone is indicated. r(C=O) is also longer in the substituted cyclo-
propenone complexes supporting the increased b&cities of these. In all cases
the C-C bonds in the complexes are shorter than in the free cyclopropenones;
also the substituted complexes (2 and 4) have the shorter bond lengths,
suggesting conjugation in the complexes and that methylation increases this
further. The C=C bond lengths are longer in the complexes in agreement
with their increase in conjugation within the cyclopropenone ring. The
r(C-H) values differ little, showing that the effects of Y on these bond
lengths is negligible. Similarly the r(C--CH3) values are the same in 2 and 4.
The B-Y distances in 1 and 2 are insignificantly different as are those in
3 and 4. However the B-F distance in BFJ is much less than in the com-
plexes (1.31 vs. 1.342 A) due to the greater possibility for s bonding in
BF+ Also, the B-F bond lengths in the complexes are less than those
calculated in BF4- (1.39 A) 151.

Gross atomic charges

The effects of the methyl groups on the complexes is to decrease the

oxygen charges as well as the carbonyl carbon charges and to increase the
charge on the remaining carbon. Thus the methyl groups push electrons into
the carbonyl which can enhance the basicities. The BF3 complexes have

TABLE‘1

Optimised geometries for R,C,O l BY,

R H CH, H CH,
Y H H F F
1 2 3 4

r(C=O) 1.211 1.215 1.217 1.223

r(C-C) 1.425 1.422 1.432 1.423
r(C=C) 1.332 1.342 1.341 1.339
r( C-H) 1.083 1.088 1.082 1.088
rlC--CH,) 1.504 1.504
W--O) 1.607 1.594 1.839 1.734
r(B-Y) 1.165 1.166 1.342 1.342
O-&Y 104.0 104.1 fOO.0 102.9
R-b 151.3 150.5 150.9 150.3
 129

TABLE 2

Gross atomic charges

R H CH, H CR,
Y H H F F
1 2 3 4

0 -6.246 -0.263 -0.288 -0.302

C(G) 0.308 0.281 0.279 0.264
c -6.039 0.020 -6.049 0.016
H 0.136 0.097 0.129 0.096
C(K) -0.184 -0.184
B 0.112 0.112 0.642 0.638
Y -0.124 -0.128 -0.264 -0.280

TABLE 3

Cumulative charges in (X,A),C,O 9 BY,

%A H CK H CBS
Y Hi H. F F
1 2 3 4

(X,)2 0.582 0.576

+A, 0.272 0.214 0.258 0.208
+C, 0.194 0.254 0.160 0.240
+C 0.502 0.535 0.439 0.504
to 0.256 0.272 0.151 0.202
i-B 0.368 0.384 0.793 0.840

lower oxygen and carbon charges, indicating that the BF3 withdraws less
charge than BE&, which is supported by the cumulative charges (Table 3); thus
as suggested previously BHs is the stronger acid in these cases. Again the
cumulative charges are greater in the R2C30 moiety of the adducts when
R = CH3.
The oxygen charges in the BH3 complexes are iess negative than in the
parent compounds whilst for the trifluoroboranes the opposite is true,
indicating the tendency for BEI3 to be a greater electron acceptor. The
carbonyl carbons are more positive in all the complexes with the BH3 adducts
being more positive than the BFJ ones and the methyl groups decreasing
the charges. The more positive charges in the complexes are a reflection
of the general eiectron donation. The increased C(0) charge with the borane
adducts is expected due to greater donation to BY, in this case, while the
decreased C( 0) charge on methylation reflects delocalisation changes.
The remaining C charges also vary, being greater in the complexes than in
the parent R&O molecules, reflecting donation in general. The C(R) charges
130

in the methyl complexes are more positive due to the electron drift to the
carbonyls and the charges in the BH3 adducts are also more positive supporting
the greater acidity of borane relative to BF3.
The B charges vary little whether R is H or CH3. However when Y = F the
boron charge is greatly increased. The boron eharges in the BF3 adducts
differ Littiefrom the value in BE’, (0.66) [ 51, showing, as is reflected in the
cumulative charges, the weak nature of the BF3 adducts, particularly when
R = H.
Charge alternation is noted in the adducts, with only minor exceptions
in the d~ethyl adducts.

Orbital populations

In the complexes the 2plr gross orbital populations for oxygen are larger
than in the parent cyclopropenones and methylation increases the 2~7~
populations. Thus the BH3 and BF3 groups pull w electrons onto the oxygen
atoms. The BH, compounds have somewhat larger 2pn gross orbital popu-
lations. Thus the 2p7rgross orbital populations support the general trend
of BH3 being a stronger acid than BF3 and methylation increasing basicity.
The G gross orbital populations of oxygen are larger for the BF3 adducts
as less donation occurs with these, as is also reflected in the charges.
The 2pn gross orbital populations for the carbon atoms differ little, while
the u values show more variation. These u values are larger in the BF3 adducts
as weaker donation occurs in these cases. Methylation increases the CT gross
orbital populations on the carbonyi carbons and decreases it on the other
carbons. Thus the crframework is ~~uen~ed by the methyl groups which
tend to push n electrons onto the oxygen and CJelectrons onto the carbonyl
carbon and away from the other carbons and oxygen.

TABLE4

Grossorbitalpopulations

R H CH, H CH3
Y H H F F
1 2 3 4

ou 6.787 6.780 6.850 6.821

on 1.459 1.483 1.438 1.481
C(G)@ 4.867 4.890 4.894 4.916
C(G)n 0.825 0.829 0.827 0.820
CU 5.179 5.115 5.183 5.118
C?l 0.860 0.865 0.866 0.866
 131

TABLE5

Total overlap populations (n values in parentheses)

R H CH, H CH,
Y H H F F
1 2 3 4

c=o 0.920 0.906 0.870 0.860

(0.279) (0.268) (0.282) (0.265)
C-C 0.646 0.644 0.640 0.644
(0.088) (0.097) (0.084) (0.097)
c=c 0.876 0.856 0.870 0.860
(0.317) (0.304) (0.316) (0.305)
C-H 0.762 0.766 0.762 0.766
C-C(K) 0.732 0.732
B-O 0.344 0.360 0.142 0.196
B-Y 0.786 0.784 0.512 0.508

Overlap populations, energies and dipole moments

The overlap populations show a decrease in both total and 7~C=C overlap
populations and an increase, also in both the total, and n, C-C overlap
populations on adduct formation, showing that complexation increases the
delocalisation. It is also of note that on methyIation the C=C total and
7~overlap populations decrease while for the C-C case, in general, the
reverse is true. Thus the overlap populations reinforce the conclusion that
methylation increases delocalisation. In the CO bond the total overlap
populations increase on complexation while the ‘ITones decrease and
methylation decreases both the total and 7rvalues.
Table 6 gives some energies and dipole moments. It is noteworthy that the

TABLE6

Energies and dipole moments

R H CH, H CH,
Y H H F F
1 2 3 4

T.E.(a.u.) -213.169 -290.359 -505.730 -582.918

I.P. (eV) 8.77 8.28 9.49 9.13
9.13 8.58 10.00 9.43
11.23 10.67 10.61 9.94
Lumo 5.79 6.30 6.09 6.39
1s orbital
Energy (a.u.) C, -11.255 -11.226 -11.226 -11.215
0 -20.362 -20.334 -20.309 -20.299
Dipole moment(D) 8.20 9.12 7.11 8.96
132

larger dimethyl adducts have the larger dipole moments. Of the cyclopropenone
adducts, the borane adduct has the larger dipole moment. This is not expected
on the basis of bond lengths but a consideration of the cumulative charges
(Table 3) shows that the H&O moiety is more positive in the BH3 case and
hence is a better electron donor. Thus the dipole moments support the
greater acidity of BH3 relative to BF3.

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