Table 2.
Calculated structural parameters of cations 2, 9 and nitrilium ions 10, 11 and silyl fluorides 12, 13 that are relevant to the discussion (M06‐2X/Def2‐TZVP). (Do‐Si: atomic distance donor atom silicon; Σβ: sum of the bay angles; d(Si), d(Do): distances of the silicon atom and donor atom from the plane that is spanned by the ten carbon atoms of the naphthalene ring, Σα(SiC3); Σα(Do): sum of the bond angles around the silicon atom and the donor atom). Experimental XRD data are given for comparison in parentheses. Cpd=compound.
|
Cpd |
Do |
Do−Si [pm] |
Σβ [°] |
Si−N [pm] |
d(Si) [pm] |
d(Do) [pm] |
Σα(SiC3) [°] |
Σα(Do) [°] |
|---|---|---|---|---|---|---|---|---|
|
2 a |
OPh |
185.4 |
337.3 |
– |
0.0 |
0.0 |
352.2 |
360.0 |
|
2 b |
SPh |
232.1 |
353.4 |
– |
18.1 |
−8.0 |
349.0 |
299.4 |
|
2 c |
SePh |
244.7 (243.1) |
357.2 (355.9) |
– |
15.6 (39.2) |
−6.8 (−0.1) |
347.9 (346.1) |
288.9 (288.4) |
|
2 d |
TeMes |
261.4 |
361.8 |
– |
5.1 |
−4.1 |
345.4 |
290.1 |
|
2 e |
Br |
247.0 |
358.4 |
– |
0 |
0 |
351.6 |
– |
|
2 f |
I |
264.3 |
363.0 |
– |
0 |
0 |
349.5 |
– |
|
9 a |
OPh |
183.2 (183.8) |
337.7 (337.9) |
– (–) |
0.6 (3.2) |
0.9 (9.5) |
351.7 (351.3) |
359.5 (360) |
|
9 e |
Br |
243.9 |
358.6 |
– |
0 |
0 |
350.7 |
– |
|
10 a |
OPh |
244.7 |
355.1 |
191.4 |
0.01 |
−0.01 |
354.8 |
360.0 |
|
10 b |
SPh |
263.6 |
361.8 |
199.9 |
27.4 |
−17.5 |
359.4 |
300.6 |
|
10 c |
SePh |
275.6 |
364.8 |
199.7 |
28.8 |
−22.2 |
358.9 |
289.3 |
|
10 d |
TeMes |
292.2 |
369.8 |
201.9 |
13.0 |
−11.3 |
359.7 |
295.5 |
|
10 e |
Br |
302.9 |
373.7 |
190.0 |
1.9 |
−1.6 |
353.9 |
– |
|
10 f |
I |
328.7 |
377.0 |
190.0 |
45.6 |
−42.9 |
355.0 |
– |
|
11 a |
OPh |
219.1 |
348.2 |
196.2 |
0.3 |
−0.1 |
357.7 |
360.0 |
|
11 c |
SePh |
267.6 |
362.4 |
201.8 |
38.3 |
−31.9 |
359.3 |
290.2 |
|
11 e |
Br |
291.4 |
369.3 |
191.0 |
38.8 |
−29.2 |
355.2 |
– |
|
12 a |
OPh |
285.8 |
367.8 |
– |
6.4 |
−7.9 |
342.4 |
349.4 |
|
12 b |
SPh |
318.2 |
378.0 |
– |
24.8 |
−16.5 |
345.2 |
289.5 |
|
12 c |
SePh |
328.5 |
380.5 |
– |
21.0 |
−17.0 |
345.6 |
280.8 |
|
12 d |
TeMes |
352.5 |
384.4 |
– |
32.5 |
−42.8 |
345.4 |
301.6 |
|
12 e |
Br |
333.2 |
381.9 |
– |
23.3 |
−12.5 |
331.2 |
– |
|
12 f |
I |
351.3 |
384.2 |
– |
42.3 |
−30.8 |
330.4 |
– |
|
13 a |
OPh |
270.7 |
363.6 |
– |
5.8 |
−6.1 |
344.4 |
355.6 |
|
13 e |
Br |
326.0 |
378.3 |
– |
49.6 |
−31.6 |
329.9 |
– |