CH2=CH-O-C(=O)Cl
























 








 









Chlorine


Nuclear Quadrupole Coupling Constants

in Vinyl Chloroformate

 








 








 

 





Chlorine nuclear quadrupole coupling constants in vinyl chloroformate were determined by Bimler et al., as well as a heavy atom substitution structure [1].

Calculation of the nqcc's was made here on this substitution structure (with CH geometries given by MP2/6-31G(d,p) partial optimization), and on a molecular structure given by MP2/aug-cc-pVTZ optimization.  These are compared with the experimental nqcc's [1] in Tables 1 and 2.  Structure parameters are given in Table 3, rotational constants in Table 4.

 








In Tables 1 and 2, subscripts a,b,c refer to the principal axes of the inertia tensor; subscripts x,y,z to the principal axes of the nqcc tensor.  Ø (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.

RMS is the root mean square difference between calculated and experimental diagonal nqcc's (percentage of the average of the magnitudes of the experimental nqcc's).  RSD is the calibration residual standard deviation of the B1LYP/TZV(3df,3p) model for calculation of the nqcc's.

 








 








   







Table 1.  35Cl nqcc's in Vinyl Chloroformate (MHz).  Calculation was made on the (1) substitution and (2) MP2/aug-cc-pVTZ structures.
   









Calc. (1)
Calc. (2)
Expt. [1]
   







Xaa -
 38.68
 -
 37.00
 -
 37.811(7)

Xbb
11.73
  9.97
  9.965(8)

Xcc
26.95
27.03
27.846(11)

|Xab| -
 51.26
 -
 52.73
 -
 51.79(26)

 







RMS
1.25 (5.0 %)
 0.66 (2.6 %)


RSD
0.49 (1.1 %)
 0.49 (1.1 %)


 







Xxx
43.65
44.21



Xyy
26.95
27.03



Xzz -
 70.60
 -
 71.24



ETA -
 0.236
 -
 0.241



Øa,z
31.91
33.00



Øa,CCl
32.86
33.59



Øz,CCl
  0.95
  0.59



 








 








 








   







Table 2.  37Cl nqcc's in Vinyl Chloroformate (MHz).  Calculation was made on the (1) substitution and (2) MP2/aug-cc-pVTZ structures.
   









Calc. (1)
Calc. (2)
Expt. [1]
   







Xaa -
 31.13
 -
 29.82
 -
 30.450(15)

Xbb
  9.89
  8.52
  8.502(15)

Xcc
21.24
21.30
21.948(22)

|Xab| -
 40.08
 -
 41.25
 -
 40.4(7)

 







RMS
0.99 (4.8 %)
 0.52 (2.6 %)


RSD
0.44 (1.1 %)
 0.44 (1.1 %)


 








 








 







 
 




Table 3. Vinyl Chloroformate.  Heavy atom structure parameters (Å and degrees).
 





rs = substitution structure, with CH geometries given by MP2/6-31G(d,p) partial optimization

ropt = MP2/aug-cc-pVTZ optimization
 






  rs
  ropt







ClC(2)
1.754
1.7422
C(2)O(3)
1.196
1.1949
C(2)O(4)
1.312
1.3422
O(4)C(5)
1.402
1.3958
C(5)C(6)
1.330
1.3264
ClC(2)O(3)
122.0
123.98
ClC(2)O(4)
108.6
108.08
O(3)C(2)O(4)
129.3
127.94
C(2)O(4)C(5)
115.7
115.76
O(4)C(5)C(6)
118.6
118.72



 








 



Table 4.  Vinyl Chloroformate.  Rotational Constants (MHz).  35Cl Species.
 




rs = substitution structure, with CH geometries given by MP2/6-31G(d,p) partial optimization

ropt = MP2/aug-cc-pVTZ optimization
 




  Calc rs Calc ropt   Expt. [1]






A 7773.1
 7698.3
 7746.511(4)

B 1630.2
 1630.4
 1626.5050(11)

C 1347.6
 1345.5
 1345.0950(10)


 








 








[1] J.Bimler, S.Broadbent, K.A.Utzat, R.K.Bohn, A.Restrepo, H.H.Michels, N.S.True, J.Mol.Struct. 1023,87(2012).


 








 








 








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Molecules/Chlorine




 








 













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Last Modified 12 Oct 2012