Supporting information for: Mechanisms and Dynamics of ... · Supporting information for: Mechanisms and Dynamics of Protonation and Lithiation of Ferrocene Nishant Sharma, ... GAUSSIAN
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Supporting information for:
Mechanisms and Dynamics of Protonation and
Lithiation of Ferrocene
Nishant Sharma, Jayanth K. Ajay, Krishnan Venkatasubbaiah, and Upakarasamy
Lourderaj∗
School of Chemical Sciences, National Institute of Science Education and Research,
a6-311++G** basis set. bDZVP basis set. cX1 is the center of the Cp ring which is closer to the H+. dX2 is the center of the Cp ring which isfarther from the H+. e∆E = EMP −EAG at different levels of theory .
S3
Tabl
eS2
:Com
pari
son
ofst
ruct
ural
para
met
ersa
ndre
lativ
een
ergi
esof
thre
edi
ffer
entt
rans
ition
stat
es.
TSb
TSa
TSd
TSc
c
BPW
91a
B3L
YPa
B3L
YPb
BPW
91a
B3L
YPa
B3L
YPb
BPW
91a
B3L
YPa
B3L
YPb
B3L
YPb
Im.F
req
(cm
−1 )
44i
29i
30i
290i
144i
308i
653i
742i
848i
48i
Fe-H
+(Å
)1.
591.
681.
711.
521.
481.
50-
--
1.48
C-H
+(Å
)1.
341.
221.
211.
571.
801.
701.
291.
281.
291.
91Fe
-X1(
Å)d
1.67
1.71
1.70
1.67
1.70
1.69
1.59
1.64
1.62
1.71
Fe-X
2(Å
)e1.
681.
711.
691.
681.
711.
701.
671.
701.
681.
70X
1-Fe
-X2
(◦)
168
169
169
168
167
167
178
178
178
159
X1-
Fe-H
+(◦
)79
7474
8794
9125
2525
98St
ruct
ure
stag
gere
dst
agge
red
stag
gere
dec
lipse
dec
lipse
dec
lipse
dec
lipse
dec
lipse
dec
lipse
dst
agge
red
∆E
f(k
cal/m
ol)
0.85
0.37
0.31
0.13
2.60
2.63
20.1
20.0
920
.29
5.16
a 6-31
1++G
**ba
sis
set.
b DZ
VP
basi
sse
t.c T
Scco
uld
notb
elo
cate
dfo
rB3L
YP/
6-31
1++g
**an
dB
PW91
/6-3
11++
g**
leve
lsof
theo
ry.d
X1
isth
ece
nter
ofth
eC
pri
ngw
hich
iscl
oser
toth
eH+
.e X
2is
the
cent
erof
the
Cp
ring
whi
chis
fart
herf
rom
the
H+
.f E
nerg
ies
rela
tive
toA
Gat
diff
eren
tlev
els
ofth
eory
.
S4
Table S3: Comparison of structural parameters and relative energies of lithiated ferroceneusing B3LYP/DZVP level of theory.
CP TSe ML TSf
Fe-Li(Å) 3.60 3.53 2.46 2.53C-Li(Å) 2.32 2.23 2.49 2.34Li-H(Å) 3.06 1.97 2.49 2.19Fe-X1(Å)a 1.64 1.68 1.69 1.70Fe-X2(Å)b 1.68 1.67 1.69 1.70C-X1-Fe-Li(◦) - - 44.15 4.01X1-Fe-Li(◦) 0.06 61.33 94 95.23Structure eclipsed eclipsed eclipsed eclipsed∆Ec (kcal/mol) 0 23.62 7.05 8.52aX1 is the center of the Cp ring which is closer to the Li+. bX2 is the center of the Cpring which is farther from the Li+. cEnergies are given relative to CP.
-60
-50
-40
-30
-20
-10
0
10
20
30
40
E MP-
E AG (k
cal/m
ol)
HF(
6-31
G*)
B
LYP(
AE1)
B
PW91
(AE1
) B
P86(
AE1D
) B
PW91
(TZP
) B
PW91
(AE1
D)
BP8
6(SV
P)
BP8
6(SV
P+)
BLY
P(TZ
P+)
BPW
91(6
-311
G)
BLY
P(SV
P+)
BLYP
(ECP
1)
BLYP
(NRE
CP1)
B
3LYP
(AE1
) C
CSD
(T)(P
VDZ)
) B
3LYP
(AE1
D)
B3L
YP(T
ZP+)
B
LYP(
LAN
L2D
Z(d)
) B
3LYP
(SVP
+)
BLY
P(LA
NL2
DZ)
B
3LYP
(6-3
11G
(f))
B3LY
P(EC
P1)
B3L
YP(6
-311
G)
CC
SD(P
VDZ)
) B
3LYP
(LAN
L2D
Z(d)
) M
P2(6
-311
g)
Fig. S1: Comparison of energy differences between metal-protonated (MP) and agostic (AG)structures in different levels of theory.
S5
TSb TSa
TSd TSc
(a)
(b)Fig. S2: (a) Structures of TSb, TSa, TSd and TSc of protonated ferrocene. (b) MEP (in a.u.) mapfor AG and MP of protonated ferrocene
S6
0
20
40
60
80
100
120
140
0 200 400 600 1200 1400 1600 1800
Popu
latio
n
800 1000
Lifetime (fs)
AG
0
20
40
60
80
100
120
140
20 40 60 80 100 120 140
Popu
latio
n
Lifetime (fs) 0
MP
(a) (b)
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Popu
latio
n
0
20
100
80
60
40
160
140
120
180
200
Lifetime (fs)
AG
0
50
100
150
200
0 50 100 150 200
Popu
latio
n
Lifetime (fs)
MP
(c) (d)
Fig. S3: Plot of population vs lifetime for agostic and metal-protonated forms when the trajectorieswere initiated from AG (a and b) and MP (c and d) minima respectively.
S7
Fig. S4: Geometries used to sample trajectories for protonation of ferrocene to represent bimolec-ular collision.
S8
(-0.003) (-0.013) (-0.018) (-0.022) (-0.03)
Fig. S5: Electrostatic potential (in a.u.) map of ferrocene for different iso-values.
Fig. S6: MEP (in a.u.) map for CP and ML of lithiated ferrocene.
S9
(Side view) (Front view)
Fig. S7: Structures of TSg connecting two ML minima.
2
2.5
3
3.5
4
4.5
0 200 400 600
Time (fs) 800 1000 1200
Dis
tanc
e (Å
)
C−Li Fe−Li
Fig. S8: Fe-Li and C-Li distance as a function of time for a representative trajectory that showsplanetary motion.
S10
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