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l 5-Bis(dimethylamino)tetrasulfur TetranitrideЦA Cage Molecule with a Non-Symmetric Nitrogen Bridge.

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[A]
Fig. I. Molecular structure of the complex (Z), showing the bond lengths
and bond angles I"] (standard deviations in brackets).
89.8(4), S-Cr-C(trans)
178.2(1)".
Mean values for 5 C-0 1.138(3), Cr-C(cis) 1.903(5) A, S-Cr-C(cis)
For the CO group in the trans position to the*sulfur
atom the Cr-C distance is shortened-to 1.846(2) A compared to the mean value of 1.903(5) A for the remaining
carbonyl ligands. The atoms Cr, S, N2 and C" are coplanar
within 0.012
and the coordination octahedron about Cr
is almost ideal. The S-N distance of 1.635(2) A corresponds to a single bond, while the N-N bond (1.278(2) A)
is markedly shortened compared to that in hydrazine derivatives (1.45 A). The bonding in the ligand can best be described in terms of the resonance structure (la).
A,
In the mass spectrum of (2) the molecular ion appears at
m/z=282 with a relative intensity of 37%. The fragmentation follows a stepwise cleavage of the CO groups, so that
Cr[SNN(CH,),] appears at m/z= 142-and with a relative intensity of 100%.
+
Procedure
(1) (0.57 g, 6.3 mmol) is treated at ca. - 15 "C with a solution of (CO)5Cr-THF(7.5 mmol) in T H F (100 ml). The
mixture is allowed to warm to room temperature, then stirred for 1 hour, the solvent removed, and the residue taken
up in 25 ml CHZCI,. After filtration and cooling, Cr(C0)6is
removed from the resulting crystalline mixture by vacuum
sublimation. Yield 0.4 g (24%) (2). decomp. = 100°C.
[2] W. J. Middleton, J. Am. Chem. SOC.88, 3842 (1966).
[3] Monoclinic, P2,/c, u= 1042.2(3), b= 1250.7(4), c=954.6(3) pm,
B= 110.21(2)", Z = 4 : automatic diffractometer (MoKn, L=71.069 pm),
2387 independent reflections with F > 3 u (F), heavy atom method;
R ~ 0 . 0 4 9 ,R, =0.044.
1,5-Bis(dimethylamino)tetrasulfur TetranitrideA Cage Molecule with a Non-Symmetric
Nitrogen Bridge'"*'
By Herbert W . Roesky, M. N . S . Rao, Cornelia GraJ
Arfed Gieren, and Erich Hadicke'']
Dedicated to Professor Marianne Baudler on the occasion
of her 60th birthday
"Substitution products" of S,N, with amino groups
have so far not been reported in the literature. We have
now found that S4N4C12(1) reacts with dimethyl(trimethy1sily1)amine (2) in the molar ratio 1 :2 to give the dimethylamino derivative (3).
(3) could be isolated in good yields as pale yellow, transparent crystals. S4N4is formed as by-product. Crystals of
(3) and their solution in CH2C12or CHC1, undergo decomposition and turn red at room temperature. However, the
crystals can be stored for months at 0 ° C without decomposition.
Received: May 22, 1980 [ Z 793a IE]
German version: Angew. Chem. 93,623 (1981)
['I
[I1 B. Buss, p. G. Jones, R . Mews, M . Noltemeyer, G. M. Sheldrrck, Angew.
Chem. 91,253 (1979): Angew. Chem. Int. Ed. Engl. 18,253 (1979): M. W
Bishop, J. Chatt, J. R . Dilworth, J. Chem. SOC.Dalton Trans. 1979, 1 ; R
MeV. T. A . M. Kaandorp, D. J. Stufkens, K . Vrreze. J. Organomet. Chem
128, 203 (1977); R. Me& D.J . Stufkens. K . Vrieze, ibid. 144, 239 (1978).
592
0 Verlag Chemie GmbH, 6940 Weinheim. 1981
Dr.H. W. Roesky 1'1, Dr. M. N. S . Rao, Dip1:Chem. C. Graf
Anorganisch-chemisches Institut der Universitat
Niederurseler Hang, D-6000 Frankfurt am Main 50 (Germany)
Dr. habil. A. Gieren
Max-Planck-Institut fur Biochemie, Abteilung fur Strukturforschung I
Am Klopferspitz, D-8033 Martinsried (Germany)
Dr. E. Hadicke
Ammoniaklaboratorium der BASF AG, D-6700 Ludwigshafen (Germany)
Author to whom correspondence should be addressed. Present address:
Anorganisch-chemisches Institut der Universitat, Tammannstr. 4,
D-3400 Girttingen (Germany)
Studies on the structure of S'"N, Groups, Part 5. This work was supported by the Deutsche Forschungsgemeinschaft. - Part 4: A. Gieren, B.
Dederer. I . Abelein, J. Anorg. Allg. Chem. 465, 191 (1980).
[*] Prof.
[**I
0570-0833/81/0707-0592 $ 02.50/0
Angew. Chem. Int. Ed. Engl. 20 (1981) No. 6/7
111
f3)
The molecule (3)(Fig. 1) exhibits only C, symmetry, and
not the possible (C2, symmetry. The two (CH3)2N-groups
are stereochemically non-equivalent. One (containing N6)
four. N5 adds nucleophilically via the lone electron pair
S3. The molecular geometry can be explained in terms of a
frozen-in intramolecular rearrangement of an (CH3)zNgroup from S1 to S3. Two sharp signals are observed in the
'H-NMR spectrum recorded at room temperature (6= 2.53
for the exo- and 6=2.35 for the endodimethylamino
group). At - 70 "C the exchange of the exo-methyl group is
frozen-in, and two broad signals appear instead of the singlet. The signal of the endodimethylamino group remains
sharp and in exactly the same position.
Procedure
A suspension of (])I9] (2.55 g, 10 mmol) in CH3CN (80
mL) is cooled, with stirring, to - 35 to - 40 C and treated
dropwise within 2.5 h with a solution of (2) (2.57 g, 22
mmol) in CH3CN (70 mL). The resulting solution is then
warmed within 2 h to room temperature. A deep-red clear
solution is obtained. After removal of solvent in a vacuum
a red oil remains. This is extracted portionwise with 100 mL
n-hexane, and the n-hexane solution is evaporated down to
60 mL. On cooling (in a deep-freeze) (3) (decomp. pt. 7072 "C) is obtained as pale-yellow crystals in 40% yield. Further amounts of (3) can be obtained by concentration of
the mother liquor. The residue insoluble in n-hexane contains S4N4 as identifiable product.
O
Received: July 7, 1980 [Z 793 b IE]
German version: Angew. Chem. 93, 624 (1981)
CAS Registry numbers:
(1). 71699-97-3; (2). 2083-91-2; (3), 78167-47-2
[A]
Fig. 1. Molecular structure of S,N4[N(CH~J2]2
(3) with bond lengths
and
angles I"] determined uia the molecular mirror symmetry. Further bond an111.8, CI-N5-C2
112.9, Nl-SI-N4
106.5,
gles are: CI-NS-Sl
N2-S3-N3
100.4, Nl-S2--S4
92.4, N2-S2-S4
92.0". Standard deviations of the determined values: bond lengths: S-S 0.002, S-N 0.0050.008, C-N 0.007-4.013 A; angles 0.2-0.7".-(3) crystallizes in the triclinic
space group Pi with a=7.559(5), b=8.496(5), c=9.480(6) A, a= 104.19(5),
8=93.4(5), y= 103.13(5)0, Z = 2 ; diffractometer data: Cu,, radiation, 1274
observed reflections (J> Zu,),corrected for absorption, measured at -60°C.
8 ,.,,=57.5", R=0.079.
occupies an exo-position on the S,N4 ring with trigonalplanar, the other (containing N5) an endo-position with
pyramidal ligand arrangement. The bond lengths in the
two SN3 groups are markedly different. The group containing S3 contains one shorter exocyclic and two longer
endocyclic S-N bonds, the group with S1 one longer exocyclic and two shorter endocyclic S-N bonds. The C2,
symmetry is also destroyed with respect to the usual S-N
bond lengths. The bonds from S2 (and S4) to N1 and N2
(and N4 and N3, respectively) are different in length. The
average S-N bond length in the S4N4ring (1.62 A), however, has almost the same size as in the S4N4 eight-membered ring of S4N>la1, S4N;[Ih1, S4N:[2a1, S4N50-IZb1,
S4N4.2C7H813],SSNP1, S5N6(CH2)4151,
S,N6(CH3)2[6a1and
SSN7Si(CH3)5[6a1,
but distinctly greater than in the Lewis
acid adducts of S4N4 with BF3[6h1,
SO,[7a1, FSOzNC0[7h1
and AsF,[*](1.588-1.599 A).
The conformation of the S4N4 ring in (3) corresponds to
that of S,N4; however, one transannular S-So bond is
opened, while the other is shortened by ca. 0.14 A to 2.447
The opened S-S bond becomes unsymmetrically
bridged by a (CH3)zN-group:N5 in the substituent forms
an S-N single bond to S1 and at the same time strong
transannular interaction with S3 (N5-S3: 2.760 A); as a
consequence the coordination number of S3 increases to
A.
a
Angew. Chem. Int. Ed. Engl. 20 (1981) No. 6 / 7
[11 a) B. D. Sharma, J . Donohue, Acta Chryst. allogr. 16, 891 (1963)); M . L.
De Lucia, P. Coppens, Inorg. Chem. 17, 2336 (1978); b) W. Flues, 0. J .
Scherer, J . Weiss, G. Wofmershauser.Angew. Chem. 88, 41 I (1976); Angew. Chem. Int. Ed. Engl. IS, 379 (1976).
I21 a) T. Chiuers. L. Fiedling. W . G. Laidlaw, M . Trsic, Inorg. Chem. 18,
3379); b) P. Luger, H. Bradaczek. R. Sreudel. Chem. Ber. 109, 3441
(1976).
131 A. Griffin,G. M . Sheidrick. Acta Crystallorg. B 31, 895 (1975), G.Ertl, J.
Weiss, 2. Anorg. Chem. 420, 155 (1976).
141 T. Chiuers, D . Proctor, J. Chem. Sac. Chem. Commsn. 197, 62; H. W.
Roesky. M . N . S . Rao, T. Nakajima, W. S. Sheldrick, Chem. Ber. 112,
3531 (1979).
I51 H . W. Roesky, C.Graf, M . N . S . Roo. B. Krebs, G. Henkel. Angew. Chem.
91, 846 (1979); Angew. Chem. Int. Ed. Engl. 18, 780 (1979).
[6] a) W. S. Shefdrick, M . N . S . Rao, H. W. Roesky, Inorg. Chem. 19, 538
(1980): b) M . G. E . Drew. D. H . Templeton, A. Zalkin, ibid. 6, 1906
(1967).
171 a) A. Gieren. E. Dederer, H. W . Roesky, N. Amin, 0. Petersen. Z . Anorg.
Allg. Chem. 440, 119 (1978); b) A. Gieren, Ch. Hahn, B. Dederer. H. W.
Roesky, N . Amin. ibid. 447. 179 (1978).
181 R. J . Gillespie, J. P. Kent, J . F. Sawyer, Acta Crystallogr. B 36, 655
(1980).
I91 L. Zboriloua. P. Gebauer. 2. Anorg. Allg. Chem. 448, 5 (1979).
Mononuclear Transition Metal Complexes
with CS,-Analogous Coordination of a Thioketene"'
By Helmut Werner, Oswald Kolb, Ulrich Schubert, and
Klaus Ackermann"'
Dedicated to Professor Siegfried Hiinig on the occasion
of his 60th birthday
Metal complexes of CS, and analogous ligands SCX
(X = 0, Se, NR etc.) are of interest as model substances for
[*] Prof. Dr. H. Werner, Dip].-Chem. 0. Kolb
Institut fur Anorganische Chemie der Universitat
Am Hubiand, D-8700 Wiirzburg (Germany)
Priv.-Doz. Dr. U. Schubert, Dipl.-Chem. K. Ackermann
Anorganisch-chemisches Institut der Technischen Universitat Munchen
Lichtenbergstr. 4, D-8046 Garching (Germany)
0 Verlag Chemie GmbH, 6940 Weinheim. 1981
0570-0833/81/0707-0593 $ 02 50/0
593
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bridge, molecules, nitrogen, dimethylamino, cage, non, symmetries, bis, tetranitrideцa, tetrasulfur
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