 To stabilize 1- so that its gas-phase acidity (ΔHacid) becomes stronger than that of

inorganic mineral acids

 To design a compact system.
 Play an important role in general acid catalysis
 Stable anions generated are useful in olefin polymerization
 Have the potential to replace halides (“toxic”) in Metal-ion batteries
 Stabilisation of highly reactive short-lived cationic species like HC60+, C6H7+, Bu3Sn+
  Strong anionic resonance i.e., delocalization of negative charge over phenyl,
naphthalene, anthracene and azulenes. (why?)
 Very strong electron withdrawing groups
 Non covalent interactions with σ or -holes.

In this work, we have employed strategies based on 1 and 3, keeping both the objectives in mind.
 2 = R1=R2=R3=R4=R4=R5=H
3 = R1=R2=R3= R4=R5= -CN
4 = R1=R2=R3= R4=R5= -Me , R6=R7=H
6(a) = R1= R3=R5= -OMe, R2= R4=R6= H, R6=R7= -Me, X=BBr3
6(b) = R1= R3=R5= -OMe, R2= R4=R6= H, R6=R7= -Me, X=BBr3
7(a) = R1=R2=R3= R4=R5= -Me, R6=R7=H, X=BBr3
7(b) = R1=R2=R3= R4=R5= -Me, R6=R7=H, X=BBr3
8(a) = R1=R2=R3= R4=R5= -Me, R6=R7=H, X=BF3
8(b) = R1=R2=R3= R4=R5= -Me, R6=R7=H, X=BF3

2,3,4,5 6(a), 7(a), 8(a) 6(b), 7(b), 8(b)

 Small size
 Strong -holes
because of the
presence of
vacant p-
orbitals
 3.128

3.220 3.135

1- 2 3 6(a) 6(b) 7(a)

3.089

2.749

2.788
3.115

4 5 7(b) 8(a) 8(b)

MESP calculations
AIM analysis
NBO analysis
1-

6(b) 7(a)
2 3

7(b)

5 6(a) 8(a) 8(b)

 Complex BCP Hr  2ρ Kr Vr Gr (-Gr/Vr)
6(a) E 0.009 0.022 -0.00079 -0.383 0.462 1.206
6(b) E 0.009 0.022 -0.00062 -0.429 0.491 1.145
F 0.008 0.021 -0.00073 -0.39 0.463 1.187
7(a) C 0.009 0.02 -0.0005 -0.409 0.459 1.122
E 7(b) C 0.01 0.022 -0.00049 -0.442 0.491 1.111
F
C
D 0.009 0.022 -0.00057 -0.431 0.489 1.135
8(a) A 0.014 0.032 -0.00016 -0.762 0.778 1.021
E
8(b) A 0.013 0.032 -0.00024 -0.745 0.769 1.032
B 0.012 0.031 -0.00062 -0.646 0.708 1.096
6(a) 6(b) 7(a)

A A

D B

7(b) 8(a) 8(b)

 Distance between Donor and
Complex Donor NBO(i) Acceptor NBO(j) E2/kcal mol-1
acceptor units/Å
6(a) BD C12-C14 LP* B35 3.22 7.82
6(b) BD C12-C14 LP* B39 3.135 6.61
BD C12-C14 LP* B35 3.134 9.05
7(a) BD C6-C8 LP* B32 3.128 11.84
7(b) BD C6-C8 LP* B32 3.089 11.5
BD C10-C11 LP* B36 3.115 10.24
8(a) BD C8-C10 LP* B32 2.737 11.06
8(b) LP C8 LP* B32 2.749 11.43
LP C10 LP* B36 2.788 13.47
 Based on the trend of gas phase acidities, if one can
create a balance between effective charge
delocalization and number of BX3 units,it is actually
possible to attain a value well below 300 kcal mol-1
or even in the range of hyperacids.