|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
C6BH6Cl
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Boron and Chlorine |
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
|
in 1-Chloroborepin |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculation of the boron
and chlorine nqcc's in 1-chloroborepin was made on a molecular structure given by B3P86/6-31G(3d,3p)
optimization, assuming C2V
symmetry. The planarity of the molecule was demonstrated by
microwave measurement of the inertial defect by Larsen et al.
[1]. Boron and nitrogen nqcc'c were subsequently measured by
Pejlovas et al. [2]. Calculated and experimental nqcc's are
compared in Tables 1 and 2. Structure parameters are given in
Table 3, rotational constants in Table 4.
|
|
|
|
|
|
|
|
|
|
|
|
|
In Tables 1 and 2, 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 model for calculation of the nqcc's:
B1LYP/6-31G(df,p) for boron, and B1LYP/TZV(3df,2p) for chlorine. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 1. Boron and Chlorine nqcc's
in 11B species of 1-Chloroborepin
(MHz). Calculation was made on the B3P86/6-31G(3d,3p) optimized
structure. The a-axis is coincident with the B-Cl bond direction,
the c-axis is perpendicular to the plane of the molecule. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc |
|
Expt [2]
|
|
| |
|
|
|
|
|
|
|
|
11B
|
Xaa |
- |
0.171 |
-
|
0.147(15) *
|
|
|
|
Xbb |
- |
2.868 |
-
|
2.987(13)
|
|
|
|
Xcc |
|
3.039 |
|
3.133(13)
|
|
|
|
|
|
|
|
|
|
|
|
RMS
|
|
0.089 (4.2 %)
|
|
|
|
|
|
RSD |
|
0.046 (2.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
35Cl
|
Xaa |
- |
38.02 |
-
|
36.381(22) **
|
|
|
|
Xbb |
|
28.92 |
|
27.739(32)
|
|
|
|
Xcc |
|
9.10 |
|
8.643(32)
|
|
|
|
|
|
|
|
|
|
|
|
RMS
|
|
1.20 (4.9 %)
|
|
|
|
|
|
RSD |
|
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
37Cl
|
Xaa |
- |
29.96 |
-
|
29.000(22) ***
|
|
|
|
Xbb |
|
22.79 |
-
|
22.100(46 )
|
|
|
|
Xcc |
|
7.17 |
|
6.900(46 )
|
|
|
|
|
|
|
|
|
|
|
|
RMS
|
|
0.70 (3.6 %)
|
|
|
|
|
|
RSD |
|
0.44 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* Derived here from experimental 1.5Xaa = -0.220(22) and 0.25(Xbb - Xcc) = -1.5300(99) MHz.
|
|
|
** Derived here from experimental 1.5Xaa = -54.572(33) and 0.25(Xbb - Xcc) = 4.7740(79) MHz. |
|
|
*** Derived here from experimental 1.5Xaa = -43.500(33) and 0.25(Xbb - Xcc) = 3.800(10) MHz. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 2. Boron and Chlorine nqcc's
in 10B, 35Cl species of 1-Chloroborepin
(MHz). Calculation was made on the B3P86/6-31G(3d,3p) optimized
structure. The a-axis is coincident with the B-Cl bond direction,
the c-axis is perpendicular to the plane of the molecule. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc |
|
Expt [2]
|
|
|
|
|
|
|
|
|
|
|
10B
|
Xaa |
- |
0.354 |
-
|
0.263(29) *
|
|
|
|
Xbb |
- |
5.948 |
-
|
6.283(77)
|
|
|
|
Xcc |
|
6.302 |
|
6.545(77)
|
|
|
|
|
|
|
|
|
|
|
|
RMS
|
|
0.250 (5.7 %)
|
|
|
|
|
|
RSD |
|
0.102 (2.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
35Cl
|
Xaa |
-
|
38.02 |
-
|
36.630(22) **
|
|
|
|
Xbb |
|
28.92 |
|
27.889(42) |
|
|
|
Xcc |
|
9.10 |
|
8.741(42)
|
|
|
|
|
|
|
|
|
|
|
|
RMS
|
|
1.02 (4.2 %)
|
|
|
|
|
|
RSD
|
|
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* Derived here from experimental 1.5Xaa = -0.394(43) and 0.25(Xbb - Xcc) = -3.207(18) MHz. |
|
|
** Derived here from experimental 1.5Xaa = -54.945(33) and 0.25(Xbb - Xcc) = 4.7870(88) MHz. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 3. 1-Chloroborepin. Molecular structure parameters, ropt (Å
and degrees). |
|
|
|
|
|
|
BC(2) |
1.5168 |
C(7)BC(2) |
125.62 |
|
C(2)C(3) |
1.3675 |
BC(2)C(3) |
127.72 |
|
C(3)C(4) |
1.4204 |
C(2)C(3)C(4) |
129.36 |
|
C(4)C(5) |
1.3683 |
C(3)C(4)C(5) |
130.10 |
|
BCl |
1.7922 |
BC(2)H |
117.42 |
|
C(2)H |
1.0893 |
C(2)C(3)H |
116.92 |
|
C(3)H |
1.0892 |
C(3)C(4)H |
114.64 |
|
C(4)H |
1.0873 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table 4. 1-Chloroborepin, 11B, 35Cl species. Rotational Constants, ropt (MHz).
|
| |
|
|
|
|
|
|
|
Calc. ropt |
Expt. [2] |
|
|
|
|
|
|
|
A |
3530.9 |
3490.905(35) |
|
|
B |
1158.9 |
1159.38520(79) |
|
|
C |
872.5 |
870.59492(56) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
[1] N.W.Larsen, S.R.Hansen, and T.Pedersen, J.Mol.Struct. 780-781,317(2006). |
|
|
[2] A.M.Pejlovas, Z.Zhou, A.J.Ashe, and S.G.Kukolich, J.Phys.Chem. A 122(6),1542(2018).
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
BH2Cl |
BCl3 |
BF2Cl |
|
|
|
Borepin |
BHCl2 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Boron |
|
|
|
|
|
Molecules/Chlorine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
1ClBorepin.html |
|
|
|
|
|
|
Last
Modified 28 Jan 2018 |
|
|
|
|
|
|
|
|
|
|