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Detection of an Orthonitrate by Vibrational Spectroscopy Na3NO4.

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C 0 M M U N I CAT10N S
The samples are sealed under argon in glass capillaries
for recording the Raman spectrum (Coderg, LRDH 800, Ar
laser, 514.5r1rn)[~],which is reproduced in the form of a line
diagram in Figure 1a.
Detection of an Orthonitrate by Vibrational
Spectroscopy: Na 3N04[**I
By Martin Jansen[*]
It has recently been shown that N a 3 N 0 3 does not exist
as orthonitrite (NO$- anion) as formerly assumed, but instead
has a structure derived from the perovskite type made up
of (NO;)ONa3['l. This suggests that Na3NO4r21 might also
be an adduct, uiz. N a 2 0 . N a N 0 3 .
All attempts to prepare single crystals of N a 3 N 0 4 suitable
for X-ray structure analysis have so far failed; however, vibrational spectroscopy should also provide unequivocal information as to whether nitrate ions are present in Na3N04.
N a 3 N 0 4 was obtained as a microcrystalline colorless
powder by heating of equimolar amounts of N a N 0 3 (analytically pure, Merck) and Na2OI3] in a sealed silver crucible
(300"C, 7d). The product is extremely sensitive to moisture and
C 0 2 , and decomposes within minutes to hydroxide and
carbonate on exposure to air.
p]
Dr. M. Jansen
Institut fur Anorganische und Analytische Chemie der Universitat
Heinrich-Buff-Ring 58, D-6300 Lahn-Giessen (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft.
534
Fig. 1. Raman spectra of a) N a n N O n and b) NaNO,.
Comparison with the Raman spectrum of N a N 0 3 (Fig.
1 b) and other nitrated5] shows that N a 3 N 0 4does not contain
NO; ions; thermal degradation to nitrites can also be ruled
out on the basis of the spectrum. instead the Raman absorptions can be interpreted assuming an orthonitrate with tetrahedral NO:- ions. A proposed assignment of the observed
vibrational frequencies is shown in Table 1. The splitting
of the vibrations v2, v3, v4, which should be degenerate in
the case of strict Td symmetry, is probably due to crystal
field effects; it can be explained by assuming DZdsite symmetry. However, a final interpretation of the spectrum requires
a knowledge of the space group of N a 3 N 0 4 and the site
symmetry of NO:-. The vibrational frequencies observed for
NF4f [61 are given for comparison in Table 1; the similarity
of the two spectra corresponds to expectations since NF:
is isoelectronic with NO:- and the atomic masses of 0 and
F are comparable. The existence of NO:- appears to apply
only to the solid state: cold 1 N sodium hydroxide decomposes
Na3N04, regenerating NO;.
Angew. Chem. Int. Ed. Engl. 16 ( 1 9 7 7 ) No. 8
Table 1. Raman spectrum of Na s N04; comparison with NF: (in NF4SbF6).
1) nBuLi, 2) Me3SiCI
H-CS-NHSiM
..-
e,
Assignment
Na 3 N04
Dzd
NF:
Td
+ LiN(SiMe3),
H-CS-OEt
(4I
(3)
Received: May 18, 1977 [Z 740 IE]
German version: Angew. Chem. 89,567 (1977)
CAS Registry numbers:
Na3N04, 62973-62-0; N aN 0 3, 7631-99-4
[l] M . Jansen, Angew. Chem. 88, 410 (1976); Angew. Chem. Int. Ed. Engl.
15, 376 (1976); Z. Anorg. Allg. Chem., in press.
[2] E. Zintl, W Morawietz,Z. Anorg. Allg. Chem. 236,372 (1938); A. Klemenc,
V Cutmann, Monatsh. Chem. 81, 361 (1950); R. Kohlmuller, Ann. Chim.
Paris [13] 4, 1183 (1959).
[3] A. Klemenc, C . Ofner, H . Wirth, Z. Anorg. Allg. Chem. 265, 221 (1951).
[4] Recorded by D. Wald.
[5] S . D. Ross: lnorganiclnfrared and Raman Spectra. McGraw-Hill,London
1972.
[6] K. 0.Chrisre, R. D. Wilson, C. J . Schack, Inorg. Chem. 16, 937 (1977).
N,N-Bis(trimethylsily1)enamines-Stereoselective Synthesis from N,N-Bis(trimethylsilyl)thiofomamide~*]
H-CS-N(SiMe,),
(a)
Me3SiCI
( I ) + Me,SiOEt
- LiCl
(b)
The structure of ( 1 ), which crystallizes as colorless needles
that are very sensitive to hydrolysis, is confirmed by its IR
and I3C-NMR spectrum (Table 1).
In contrast to the thiophilic addition generally observed
on attack of organolithium compounds ( 5 ) on thiocarbonyl
groups[4], these compounds react with ( I ) by carbophilic
addition to form the salts ( 6 ) . Carbophilic addition was also
detected in the reaction of phenyllithium with N,N-dimethylthiobenzamide or -thi~formamide~~'.
Reaction of (6) with
trimethylchlorosilane gives the 1-(trimethylsilylthio)-N,N-bis(trimethylsily1)alkylamines (7), which decompose spontaneously by elimination of trimethylsilanethiol (8) into the
N,N-bis(trimethylsily1)enamines ( 9 ) . Compound ( 8 ) condenses immediately with elimination of H2S to give hexamethyldisilathiane (
(I)
i
RCH,Li
+
-
r
SLi
H-C-N(SiMe,),
I
(5)
-I
S-SiMe,
CHzR
I
By Wolfgang Walter and Hans- Wolfgang Liikepl
Monosilylated enamines have only recently been described['! In the course of our studies on silylated thioamides[']
we have now prepared the hitherto unknown N,N-bis(trimethylsily1)enamines ( 9 ) and (13), which are of preparative interest
as masked N-unsubstituted enamines.
The starting material ( 1 ) was obtained as the first bis-silylated thioamide by metalation and silylation of N-trimethylsilylthioformamide (2)['"] [eq. (a)] or alternatively by reaction
of 0-ethyl thioformate (3)I31 with lithium bis(trimethylsily1)amide ( 4 ) [eq. (b)].
t
(7)
-
R\Z I,H
,C=C
H
+ [Me3SiSH]
\N(SiMe3)2
(9)
(a): R = H
( b ) : R = CH,
( c ) : R = nC,H.,
(8)
pzs
1 / 2 (Me, Si),S
(10)
Table 1. Properties of the new compounds
Compound
B.p.
["Cltorr]
49-5OjO.05
(1)
IR [a;
[cm-
1
"C-NMR [c]
'H-NMR [b]
6 rel. to TMS
vNSiz 882
9.90 (s) HCS, 0.40 (s) HCSi
205.9 CS, 1.5 CSi
(9al
1361760
vC=C 1610
vNSiz 935
6.13 (dd, 3J t , =1 6 H ~ ,3J,,,=8Hz) 1-H.4.27 (d, 'J,,,=
8Hz) H(R), 4.18 (d, 'J,,=16Hz) 2-H, 0.16 (s) HCSi
140.8 C-1, 97.9 C-2, 1.9 CSi
(96)
52/10
vC=C 1645
vNSiz 942
5.85 (dq, 3J,,=13.5Hz,4J=1.6H~)l-H,4.94(dq,
3JJ,,=13.5H~,
3 J = 6 . 5 H ~ 2-H,
)
1.61 (dd, ' J =
6.5Hz. ' J = 1.6Hz) 2-CHp, 0.14 (s) HCSi
134.2 C-1, 115.3 C-2, 14.9 C(R), 1.8 CSi
(9c)
7114.2
vC=C 1640
vNSi, 945
5.93 (dt, 'Jt,=13.6Hz, "J=1.1 Hz) 1-H, 5.07 (dt,
3J,,=13.6Hz, 3 J = 7 H ~ 2-H,
)
1.93 (qt, 'J=7Hz. 4 J =
1.1 Hz) H'(R), 1.35 (sexd, 3 J =7 H z , 4 J = 1 . 3 H ~H'(R),
)
0.90 (t. ' J = 7 Hz) H3(R), 0.17 (s) HCSi
133.7 C-1, 121.0 C-2, 32.4 C'(R),
23.6 Cz(R), 13.6 C'(R), 1.9 CSi
(11)
9810.04
vNSi, 945
7.2-7.7 (m) H(Ph), 5.83 (s) HC, 0.30 (s) MeSiS,
0.12 (s) MeSiN
64.2 C-1, 145.6 Ph', 128.4 Ph'.',
127.3 Ph4, 4.0 MeSiS, 3.4 MeSiN
(13)
6610.008
vC=C 1636
vNSi2 930
6.36 (dt, 'JJ,,=13.6Hz, 4 J = l . i Hz) 1-H, 5.15 (dt,
'.Ic,=
13.6 Hz, 'J=7.3 Hz) 2-H, 3.26 (dd, 'J=7.3 Hz,
4 J = l . l Hz) CH2, 0.33 (s) MeSiS, 0.19 (s) MeSiN
136.0 C-1, 114.5 C-2, 27.6 CHz,
1.0 Me'SiS, 2.0 Me3SiN
[a] Characteristic bands.
[b] ( I ) , (9a), and (11) in CCI4; (9b) and ( 1 3 ) in CDClp; (9c) in C6D6.
[c] All spectra in CDC13: assignments supported by off-resonance spectra.
[*I Prof. Dr.
['"I
W. Walter, Dip1.-Chem. H.-W. Luke
Institut f i r Organische Chemie und Biochemie der Universitat
Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (Germany)
This work was supported by the Deutsche Forschungsgemeinschaft.
Angew. Chem. Int.
Ed. Engl. 16 (1977) No. 8
Compound ( 9 ) exists exclusively in the E form. We were
unable to detect an enamine-imine tautomerism due to metallotropism of the kind observed in stannyl-substituted enamines['].
535
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