Table I. Comparative bond lengths (Å) and angles (°) of the A1 and A5 conformers
Tau.
|
Method
|
B3LYP/
6-311++G
|
B3LYP/
6-311++G
(2df,2p)
|
B3LYP-
cc-pVTZ
|
wB97X-D/
6-311++G
(2df,2p)
|
wB97X-D/
cc-pVTZ
|
B3LYP-
6-311++G
(2df,2pd)a
|
Micro-waveb
|
X-rayc
|
Δ%*
|
Δ%**
|
A1
|
d C4 = O6
|
1.212
|
1.210
|
1.209
|
1.207
|
1.205
|
1.209
|
1.219
|
1.239
|
0.8
|
2.4
|
|
d C4 ̶ N2
|
1.361
|
1.357
|
1.357
|
1.357
|
1.354
|
1.357
|
1.352
|
1.326
|
0.4
|
2.3
|
|
d N2 ̶ H1
|
1.007
|
1.004
|
1.004
|
1.005
|
1.002
|
1.004
|
1.002
|
1.010
|
0.2
|
0.6
|
|
d N2 ̶ H3
|
1.009
|
1.007
|
1.006
|
1.007
|
1.005
|
1.007
|
1.002
|
1.010
|
0.4
|
0.4
|
|
d C4 ̶ H5
|
1.106
|
1.104
|
1.105
|
1.105
|
1.104
|
1.104`
|
1.098
|
1.090
|
0.6
|
1.4
|
|
< O6C4N2
|
124.93
|
124.88
|
125.01
|
124.78
|
124.86
|
124.9
|
124.7
|
124.9
|
0.3
|
0.09
|
|
< H3N2C4
|
119.44
|
119.44
|
119.37
|
119.20
|
119.24
|
119.4
|
118.5
|
118.0
|
0.7
|
1.2
|
|
< H1N2C4
|
121.40
|
121.38
|
121.36
|
121.42
|
121.35
|
121.3
|
120.2
|
119.0
|
1.0
|
2.0
|
|
< H5C4O6
|
12.67
|
122.63
|
122.81
|
122.64
|
122.74
|
122.6
|
122.6
|
-
|
|
-
|
|
< N2C4H5
|
112.30
|
112.49
|
112.18
|
112.58
|
112.40
|
112.5
|
112.7
|
116.0
|
0.5
|
3.3
|
|
< H1N2H3
|
119.16
|
119.18
|
119.27
|
119.38
|
119.42
|
119.2
|
121.5
|
-
|
|
-
|
A6
|
d C1 ̶ O3
|
1.347
|
1.345
|
1.346
|
1.337
|
1.338
|
1.362
|
-
|
-
|
-
|
|
d C1 = N4
|
1.263
|
1.259
|
1.259
|
1.258
|
1.257
|
1.254
|
-
|
-
|
-
|
|
d N4 ̶ H6
|
1.016
|
1.014
|
1.014
|
1.012
|
1.013
|
1.020
|
-
|
-
|
-
|
|
d O3 ̶ H5
|
0.970
|
0.969
|
0.969
|
0.964
|
0.965
|
0.963
|
-
|
-
|
-
|
|
d C1 ̶ H2
|
1.091
|
1.088
|
1.089
|
1.089
|
1.089
|
1.089
|
-
|
-
|
-
|
|
< O3C1N4
|
122.19
|
122.28
|
122.26
|
122.19
|
122.16
|
-
|
-
|
-
|
-
|
|
< H6N4C1
|
111.66
|
111.95
|
111.58
|
111.54
|
111.18
|
111.7
|
-
|
-
|
-
|
|
< H45O3C1
|
107.12
|
107.33
|
106.74
|
107.32
|
106.71
|
110.5
|
-
|
-
|
-
|
|
< H2C1O3
|
110.14
|
110.25
|
110.06
|
110.65
|
110.52
|
114.7
|
-
|
-
|
-
|
|
< H2C1N4
|
127.67
|
127.47
|
127.68
|
127.16
|
127.32
|
120.6
|
-
|
-
|
-
|
* Percentage of error (Δ%): between wB97X-D/cc-pVTZ (This Work) and Microwave.
** Percentage of error (Δ%): between wB97X-D/cc-pVTZ(This Work) and X-ray.
a Ref. [26].
b Ref. [28]
c Ref. [29].
Table II not available with this version
Table III. Comparative bond lengths (Å) and angles (°) of the C1 and C3tautomersbased on B3LYP/cc-PVTZ method
Conformer
|
Method
|
B3LYP-cc-pVTZ
|
Conformer
|
Method
|
B3LYP-
cc-pVTZ
|
C1
|
d C1 = O2
|
1.189
|
C3
|
d C1 ̶ O2
|
1.342
|
|
d C1 ̶ N3
|
1.347
|
|
d C1 = N3
|
1.244
|
|
d N3 ̶ H5
|
1.003
|
|
d N3 ̶ H5
|
1.015
|
|
d N3 ̶ H4
|
1.003
|
|
d O2 ̶ H4
|
0.966
|
|
d C1 ̶ F6
|
1.363
|
|
d C1 ̶ F6
|
1.344
|
|
< O2C1N3
|
129.06
|
|
< O2C1N3
|
120.02
|
|
< H4N3C1
|
121.08
|
|
< H5N3C1
|
111.30
|
|
< H5N3C1
|
118.68
|
|
< H4O2C1
|
109.71
|
|
< F6C1O2
|
121.73
|
|
< F6C1O2
|
110.55
|
|
< N3C1F6
|
109.21
|
|
< F6C1N3
|
120.43
|
|
< H5N3H4
|
120.24
|
|
|
|
Table IV. Relative Energies (kJ.mol-1) of fluoro-formamide tautomers (by B3LYP/cc-PVTZ method)
Energy from
|
∆E SCF (kJ/mol)
|
∆H (0K)
|
∆H (298K)
|
∆G (298K)
|
C1
|
-706947
|
-706847
|
-706834
|
-706918
|
C2
|
-706892
|
-706794
|
-706782
|
-706863
|
C3
|
-706855
|
-706755
|
-706742
|
-706823
|
C4
|
-706854
|
-706754
|
-706742
|
-706823
|
C5
|
-706847
|
-706746
|
-706734
|
-706814
|
C6
|
-706836
|
-706735
|
-706723
|
-706804
|
C7
|
-706667
|
-706568
|
-706556
|
-706636
|
C8
|
-706654
|
-706556
|
-706543
|
-706625
|
C9
|
-706641
|
-706546
|
-706533
|
-706616
|
C10
|
-706642
|
-706544
|
-706531
|
-706613
|
C11
|
-706635
|
-706539
|
-706525
|
-706607
|
C12
|
-706629
|
-706534
|
-706521
|
-706603
|
Table V. Relative Energies (kJ.mol-1) of fluoro-formamide transition states (by B3LYP/cc-PVTZ method)a
Energy from
|
∆E SCF (kJ/mol)
|
∆H (0K)
|
∆H (298K)
|
∆G (298K)
|
D1
|
97.06
|
91.58
|
91.51
|
95.74
|
D2
|
104.50
|
97.68
|
98.42
|
103.44
|
D3
|
107.31
|
101.81
|
101.78
|
105.97
|
D4
|
290.67
|
285.44
|
286.01
|
289.87
|
D5
|
295.35
|
290.68
|
291.09
|
294.55
|
D6
|
360.91
|
353.89
|
354.03
|
358.08
|
D7
|
370.54
|
364.52
|
364.66
|
368.54
|
D8
|
433.87
|
425.82
|
426.83
|
431.30
|
D9
|
49.45
|
43.55
|
44.10
|
44.85
|
D10
|
133.59
|
125.11
|
126.05
|
126.42
|
D11
|
142.00
|
134.83
|
135.55
|
136.26
|
D12
|
193.07
|
178.29
|
180.18
|
180.77
|
D13
|
210.50
|
195.34
|
197.28
|
197.81
|
D14
|
241.91
|
234.70
|
236.00
|
236.23
|
D15
|
247.43
|
241.41
|
242.17
|
242.82
|
D16
|
464.16
|
455.55
|
456.49
|
458.82
|
D17
|
485.96
|
476.36
|
477.37
|
479.57
|
D18
|
558.00
|
543.18
|
545.19
|
547.67
|
D19
|
561.26
|
545.61
|
547.66
|
550.06
|
Table VI. Gibbs free energy (∆G) (kJ/mol) for possible tautomerisms of fluoro-formamide and fluoro-formamidic acid (at 298 K)
