RR'SbCl (
1) and RR'BiCl (
2) [R = 2-(Me
2NCH
2)C
6H
4, R' = CH(Me
3Si)
2] form by the reaction of R'ECl
2 (E = Sb,Bi) with RLi. The reaction of
1 with LiAlH
4 and metalation with
n-BuLi gives RR'SbH (
3) and RR'SbLi·2THF (
4)(THF = tetrahydrofuran). Transmetalation of
4 with sodium
tert-butoxide in the presence of TMEDA (TMEDA =tetramethylethylenediamine) leads to RR'SbNa·TMEDA (
5). Structural analyses by
1H NMR in C
6D
6, C
6D
5CD
3, or(CD
3)
2SO with a variation of the temperature (
1,
2,
4, and
5) and by single-crystal X-ray diffraction (
1,
2,
4, and
5) revealed the intramolecular coordination of the pendant Me
2N group on the pnicogen centers in
1 and
2 and onLi or Na in
4 or
5. The variable-temperature
1H NMR spectra of the hydride
3 in C
6D
6, C
6D
5CD
3, or (CD
3)
2SO showthat the pyramidal configuration on antimony is stable up to 100
![](/images/entities/deg.gif)
C, whereas inversion at the nitrogen is notprevented by internal coordination even at -80
![](/images/entities/deg.gif)
C. The crystals of
1,
2,
4, and
5 consist of discrete molecules withthe Sb and Bi atoms in an approximately
![](/images/gifchars/Psi.gif)
-trigonal-bipyramidal environment in the cases of
1 and
2 and in apyramidal environment in the cases of
4 and
5. Crystal data for
1: triclinic, space group
P![](/images/entities/onemacr.gif)
,
a = 7.243(4) Å,
b =10.373(3) Å,
c = 15.396(5) Å,
![](/images/gifchars/alpha.gif)
= 79.88
![](/images/entities/deg.gif)
,
![](/images/gifchars/beta2.gif)
= 78.27
![](/images/entities/deg.gif)
,
![](/images/gifchars/gamma.gif)
= 71.480(10)
![](/images/entities/deg.gif)
,
V = 1066.2(7) Å
3,
Z = 2,
R = 0.0614.
2: monoclinic, space group
P2
1/
n,
a = 10.665(2) Å,
b = 14.241(2) Å,
c = 14.058(2) Å,
![](/images/gifchars/beta2.gif)
= 90.100(10)
![](/images/entities/deg.gif)
,
V =2135.1(6) Å
3,
Z = 4,
R = 0.049.
4: monoclinic, space group
P2
1/
n,
a = 11.552(2) Å,
b = 16.518(3) Å,
c =15.971(5) Å,
![](/images/gifchars/beta2.gif)
= 96.11(2)
![](/images/entities/deg.gif)
,
V = 3030.2(12) Å
3,
Z = 4,
R = 0.0595.
5: monoclinic, space group
P2
1/
n,
a =9.797(2) Å,
b = 24.991(5) Å,
c = 14.348(3) Å,
![](/images/gifchars/beta2.gif)
= 94.98(3)
![](/images/entities/deg.gif)
,
V = 3499.66(12) Å
3,
Z = 4,
R = 0.0571. Thedissociation of the intramolecular N-pnicogen bond and inversion at the nitrogen occurs when solutions of
1 or
2in C
6D
6 or C
6D
5CD
3 are heated above 25 or 30
![](/images/entities/deg.gif)
C.
1 and
3-
5 are stable with respect to inversion of the configurationat the antimony in C
6D
6, C
6D
5CD
3, or (CD
3)
2SO up to 160
![](/images/entities/deg.gif)
C. Bismuth inversion, probably via the
edge mechanism,is observed in solutions of
2 in (CD
3)
2SO at 45
![](/images/entities/deg.gif)
C but not in C
6D
5CD
3 below 125
![](/images/entities/deg.gif)
C.