Psuedopelletierine:  9-Methyl-9-Azabicyclo[3.3.1]nonan-3-one


 








 








 








Nitrogen


Nuclear Quadrupole Coupling Constants


in Pseudopelletierine


 








 








 








Calculation of the N nqcc tensors was made here on molecular structures of axial and equatorial, chair-chair conformers of pseudopelletierine optimized at the B3P86/6-31G(3d,3p) and PBE1PBE/6-31G(3d,3p) levels of theory, and for the axial conformer on reSE structure of Vallejo-Lpez [1].  Calculation of the molecular PE at the B3PW91/6-311+G(df,pd) level of theory on these optimized structures gives Eax < Eeq by about 2.1  kJ/mol.  Calculated and experimental nqcc's are compared in Tables 1 - 3, rotational constants in Table 4.

 









ax

eq












































 








In Tables 1 - 3, 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.  ETA = (Xxx - Xyy)/Xzz.   (degrees) is the angle between its subscripted parameters.  z,N-Me is the angle between the N-CH3 bond direction and the external z-axis.

RMS is the root mean square difference between calculated and experimental diagonal nqcc's (percent of the average of the magnitudes of experimental nqcc's).  RSD is the residual standard deviation of the B3PW91/6-311+G(df,pd) model for calculation of the efg's/nqcc's.


 









 








   








Table 1. 14N nqcc's in axial Pseudopelletierine (MHz).  Calculation was made on the (1) B3P86/6-31G(3d,3p) and PBE1PBE/6-31G(3d,3p) opt structures.
   










Calc (1)

Calc (2)
Expt [1]

   








Xaa -
3.208 -
3.210
-
3.4639(51)


Xbb
0.566
0.574

0.8658(59)


Xcc
2.642
2.636

2.5982(59)


|Xab|
3.848
3.836




 







RMS

0.229 (9.9 %)

0.224 (9.7 %)




RSD

0.030 (1.3 %)

0.030 (1.3 %)












Xxx
2.965
2.959




Xyy
2.642
2.636



Xzz - 5.607 -
5.595




ETA - 0.0575 -
0.0578




z,a
  31.9

  31.9




a,N-Me
  73.3

  73.4




z,N-Me
105.2

105.3




 







   








 








   
 






Table 2. 14N nqcc's in axial Pseudopelletierine (MHz).  Calculation was made on the reSE structure.
 
 









Calc (2)
Expt [1]

 
 






14N Xaa -
3.347
-
3.4639(51)



Xbb
0.769

0.8658(59)



Xcc
2.578

2.5982(59)



|Xab|
3.660





 






RMS

0.088 (3.8 %)





RSD

0.030 (1.3 %)












Xxx
2.909





Xyy
2.578




Xzz - 5.488





ETA - 0.0603





z,a
  30.3





a,N-Me
  75.8





z,N-Me
106.1





 


























   








Table 3. 14N nqcc's in equatorial Pseudopelletierine (MHz).  Calculation was made on the (1) B3P86/6-31G(3d,3p) and PBE1PBE/6-31G(3d,3p) opt structures.
   










Calc (1)

Calc (2)
Expt [1]

   








Xaa
1.888
1.897

1.935(11)


Xbb -
4.574 -
4.576
-
4.496(36)


Xcc
2.686
2.679

2.561(36)


|Xab|
2.843
2.823




 







RMS

0.089 (3.0 %)

0.085 (2.8 %)




RSD

0.030 (1.3 %)

0.030 (1.3 %)












Xxx
2.961
2.955




Xyy
2.686
2.679



Xzz - 5.647 -
5.634




ETA - 0.0487 -
0.0490




z,a
110.7
110.5




a,N-Me
    5.2

    5.0




z,N-Me
105.5

105.5




 








 








 








Optimized structures of these conformers are given in Z-matrix format here:  axial and equatorial.


 













Table 4.  Pseudopelletierine .  Rotational Constants (MHz) and Dipole Moments (D).  Calc (1) = B3P86/6-31G(3d,3p) and Calc (2) = PBE1PBE/6-31G(3d,3p) opt structures.

 



______________axial_______________

 




Calc (1)
Calc (2)     Expt [1]

 



A  1403.
 1405.
1391.70329(70)

B  1194.
 1196.
1190.60002(10)

C  1037.
 1039.
1032.058673(91)

 



|a|  2.93
 2.91


|b|  0.68
 0.68


 



____________equatorial_____________

 



A  1673.
 1675.
1669.11(16)

B  1022.
 1024.
1014.416063(96)

C  1012.
 1014.
1006.893694(96)

 



|a|  3.57
 3.56


|b|  0.15
 0.15








 








 








[1] M.Vallejo-Lpez, P.cija, N.Vogt, J.Demaison, A.Lesarri, F.J.Basterretxea, and E.J.Cocinero, Chem.Eur.J. 23,16491(2017).


 









M.Vallejo-Lpez, P.Ecija, E.J.Cocinero, A.Lesarri, F.J.Basterretxea, and J.A.Fernndez, Abstract MI08, 71st International Symposium on Molecular Spectroscopy, Champaign-Urbana, Ill 2016.


 









 









Tropinone
Tropane
1-Asabicyclo[2.2.2]octane

boat-chair Pseudopelletierine






 









 








Table of Contents




Molecules/Nitrogen




 








 













PP_cc.html






Last Modified 30 Nov 2017