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Coordination of Dimethyl(thionitroso)amine to Pentacarbonylchromium via the Sulfur Atom.

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Acta Chem. Scand. 17, 1683 (1963); R. Baker. P. J. Garratr, K . C. Nicolaon. F. Sondheimer, Tetrahedron Lett. 1972, 3425.
[5] J. A . Elurdge. R . P. Linstead, B. A. Orkin, P. Sinis, H . Baer. D . B. Pattison, J. Chem. SOC.1950,2232.
161 K . Kratzat. Dissertation, Universitat Heidelberg 1979.
[71 As a model compound, 2,2-dibromo-l -methylcyclopropanecarboxylic
acid was reacted with tBuLi under the same conditions. Only one stereospecific Br/H-exchange process, leading to ethyl trans-2-bromo- I-methylcyclopropanecarboxylate,occurred. This shows that an extraordinary
stable carbanion is formed syn to the ester function, a fact which is in accord with the stereochemistry of both cyclization products (7) and (9).
[8] Space group P2,/c; a=801.4, b = 1073.7, c= 1221.4 pm, p=97.55"; Z = 4 ,
=2.04 g.cm-'. The structure was solved by direct methods with a
multi-solution technique. [ G . Gemtain, M . M . Woolfon. Acta Crystallogr.
B24,91 (1968); see also H . W. Kaufmann, L. Leiserowitz, ibid. 826,442
(1970)l. The positions of the H atoms were obtained from the IFo- F,I difference map. The refinement with 2531 reflections (of which 589 were
unobserved) converged to an R-factor of 5.2%.
191 Elemental Analysis and mass spectrum (molecular peak at m/e=380)
gave the summation formula C12H12BrZ04.
'H-NMR: 6=1.35 (s, 3H,
C H 3 ) , 2.69 (s, 1 H), 3.81 (s, 3H, O m > ) ;"C-NMR: 6= 169.40 ( M ) ,
52.19 (OCH,), 49.60 (quart. C), 45.71 (quart. C), 39.02 (CH),19.01
(a,).
A Diorganotin Oxide
with a Planar Tin-Chalcogen Six-Membered Ring[**'
By Heinrich Puff, WiIIi Schuh, Rolf Sievers,
and Rene Zimmer"]
Dedicated to Professor Rolf Appel on the occasion of his
60th birthday
The properties of most diorganotin oxides would indicate polymeric structures"]. Although molecular weight determinations indicated presence of trimers in solution in
the case of di-tert-butyltin oxide"] Chu and Murray assumed a polymeric structure in the solid state on account
of the sparing solubility of the sample.
O n reaction of tBu2SnC12 with sodium hydroxide in
boiling toluene we were able to obtain a form of the ditert-butyltin oxide which is readily soluble in organic solvents in the cold and is therefore obviously of low molecular weight.
The compound crystallizes hexagonally in the space
group Rk-D;,, a = 1035, c=5144 pmc3].The unit cell contains six molecules (tBu2SnO)3. As shown by the X-ray
structure analysis[41( R = 0.045), tin and oxygen atoms are
coupled to a planar six-membered ring.
there are either puckered ~ix-rnembered[~~I
or four-memberedLsblrings, or open chainsiSC1.The Sn-0 bond lengths
are of about the same order of magnitude as in comparable
compounds with distinctly tetravalent tin, e. g.
Ph3Sn-0-SnPh,
(195 to 196 pm)16]. In contrast to other
S n O - c o m p ~ u n d s [a~n~association
,
of the molecules with an
increase in the bond numbers of tin and oxygen is not observed; the shortest intermolecular Sn-0 distance is 644
Pm.
Received: August 5, 1980 [Z 792 IE]
German version: Angew. Chem. 93, 622 (1981)
[I] W. P. Neumann: Die Organische Chemie des Zinns, F. Enke Verlag,
Stuttgart 1967, p. 133.
121 C. K . Chu. J. D . Murray, J. Chem. SOC.A 1971, 360.
[3] The same compound was obtained by A. Tzschach and M . Driger(private
communication).
[4] Measurements at - 85°C; four-circle diffractometer CAD 4, program
system X-RAY 76, IBM/370-168 computer at the Regionales Hochschulrechenzentrum, Universitat Bonn.
[S] Cf. a) A . Blecher. M. Drager. Angew. Chem. 91, 740 (1979); Angew.
Chem. Int. Ed. Engl. 18,677 (1979); and references cited therein.-b) H.
PuH.R. Gatfermayer, R. Hundt, R . Zimmer, ibid. 89, 556 (1977) and 16,
547 (1977);-c) H. puff; A. Bongartz, R . Sieuers, R . Zimmer. ibid. 90,995
(1978) and 17, 939 (1978).
[6] C . Glidewell, D . Liles. Acta Crystallogr. B 34, 1693 (1978).
[7] Compounds of type [(RRSnX)20]z:P. G. Harrison, M . J. Begley. K . C .
Molloy, J . Organomet. Chem. 186, 213 (1980): R = R = C H 3 , X=CI; H.
Pufi E. Friedrichs, F. Vise!, Z. Anorg. Allg. Chem., in press:
R=R=CH(CH3)2,X=CI and R=C(CH,),, R=CH2Si(CH3),,X=OH.
Coordination of Dimethyl(thionitroso)amine to
Pentacarbonylchromium via the Sulfur Atom[**]
By Herbert W. Roesky, Ray Emmert, William Clegg,
Wilhelm Isenberg and George M. Sheldrick"'
Dedicated to Professor Josef Goubeau on the occasion
of his 80th birthday
In all complexes of acyclic sulfur-nitrogen compounds
known so far the N-S ligands are coordinated to the metal via nitrogen atoms[''. Reaction of the unstable dimethyl(thionitroso)amine (1/[21-prepared from dimethylhy//S
H3C,
N-N
H&'
Bond length [pm]
196
219
Sn-0
Sn-C
Angle ["I
0-Sn-0
Sn&Sn
C-Sn-C
106.9
133.1
119.9
Such a planar arrangement has so far not been detected
in the case of diorganotin-chalcogen compounds; in the
analogous sulfur, selenium, and tellurium compounds
[*I Prof. Dr. H. Puff, Dr. R. Sievers, Dr. R. Zimmer, W. Schuh
[*'I
Anorganisch-chemisches Institut der Universitat
Gerhard-Domagk-Str. I, D-5300 Bonn (Germany)
This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
Angew. Chem. Int. Ed. Engl. 20 (1981) No. 6/7
+ ( C O ) S C r - T H F +(CH3)2N2S-Cr(CO)S + T H F
(1)
(2)
drazine and sulfur-with (CO)&r, T H F in tetrahydrofuran
(THF) affords the 1 : 1 complex (2), which we isolated as
ruby-red crystals, stable at room temperature. As shown by
a n X-ray structure analysis[31,the SN ligand in (2) is bound
to chromium via the sulfur atom (Fig. 1).
[*I Prof. Dr. H. W. Roesky ['I, R. Emmert
Anorganisch-chemisches Institut der Universitat
Niederurseler Hang, D-6000 Frankfurt am Main 50 (Germany)
Prof. Dr. G . M. Sheldnck, Dr. W. Clegg, DipLChem. W. Isenberg
Anorganisch-chemisches Institut der Universitat
Tammannstr. 4, D-3400 Gottingen (Germany)
['I
Author to whom correspondence should be addressed. Present address:
Anorganisch-chemisches Institut der Universitat, Tammannstr. 4, D3400 Gottingen (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft and
Hoechst AG.
0 Verlag Chemie GmbH, 6940 Weinheim. 1981
0570-0833/81/0707-0591 $ 02.50/0
591
[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
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thionitroso, pentacarbonylchromium, coordination, atom, amin, sulfur, dimethyl, via
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