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An Alkylsulfur Imide Amide (Methanesulfinamidine)ЧRelation between Coordination Number and Bond Length.

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able from the S12molecule (left and right halves of the molecule
in Fig. 1).
Although no unusually long or short bonds are present, an
alternation of bond lengths symmetric to one of the C 2 axes is
clearly recognizable. This can be interpreted in terms of the
alternating torsion angles which have the value 123+2 or
-77*2", the greater value leading to a weakening of the
SS bonds which then gives rise to a slight shortening of
the neighboring bonds owing to strong bond-bond interacti0n[~1.The lower thermal stability of Slo compared to that
of S8 and S I 2 can be attributed to the four large torsion
angles of ca. 123", which exceed the previously observed values
in sulfur rings by more than 20". This results in a stronger
electron pair repulsion between neighboring atoms and thus
a decrease in bond energy17'. The smallest intermolecular
distance between nuclei is 323 pm.
Hence the structures of the sulfur homocycles S, with n =6,
7, 8, 10, 12, 18, and 20 are now known.
the molar ratio 2: 1 to give the sulfur diamide ( 2 ) . On treatment with an additional amount of SC12 compound ( 2 )
affords the methylsulfur imide amide (3). Alkylation of sulfur
with cleavage of a R3Sn group was observed for the first time
in this reaction.
2 CF3S02N[Sn(CH3),], + SCl,
+
(1)
CF,S02-N
S
/ \ N-S02CF3
I
+
2 (CH,),SnCl
I
(CH3)$5n Sn(CH3),
(2)
Received: November 17, 1977 [Z 876b IE]
German version. Angew. Chem. 90,55 (1978)
CAS Registry number:
Slo, 12597-15-8
[1]
[2]
[3]
[4]
[5]
[6]
[7]
Part 54 of Sulfur Compounds. This work was supported by the Deutsche
Forschungsgemeinschaft.-Part 53: R. Steudel, H . 4 . Muusle, Angew.
Chem. 90,54 (1978); Angew. Chem. Int. Ed. Engl. 17.56 (1978).
M . Schmidt, B. Block, H . D. Block, H . KOpL E. Wilhelm, Angew. Chem.
80, 660 (1968); Angew. Chem. Int. Ed. Engl. 7, 632 (1968).
U . 4 . Zdhorszky, Angew. Chem. 80, 661 (1968); Angew. Chem. Int. Ed.
Engl. 7, 633 (1968).
R. Steudel, F . Schuster, unpublished; F . Schuster, Diplomarbeit, Technische Universitat Berlin 1976.
R. Steudel, J . Steidel, 7: Sandow, unpublished.
F. Tuinstra, J. Chem. Phys. 46, 2741 (1967); J . Kao, N . L. Allinger,
Inorg. Chem. 16, 35 (1977).
Review: R. Steudel, Angew. Chem. 87, 683 (1975); Angew. Chem. Int.
Ed. Engl. 14, 655 (1975).
The white crystalline product (3) could not be unequivocally characterized by elemental analysis, mass spectrum, 'Hand 19F-NMR spectra (the structure of a N-methyl derivative
of type ( A ) could not be ruled out).
In addition to proving the structure, X-ray analysis provided
further information. On the one hand, conventional formulation with alternate single and double bonds, as shown for
( 3 ) , is unsuitable for describing the actual bonding. A correlation apparently exists between the bond lengths and the coordination numbers (CN) of the participating atoms (cf. Fig.
1).
An Alk ylsulfur Imide Amide (Methanesu1finamidine)Relation between Coordination Number and Bond
Length[**]
1.81/
By Herbert W Roesky, Manfred Diehl, Hartmut Fuess, and
Jan Willem Batspl
Reaction of sulfur dichloride with nitrogen-containing
organometallic compounds is a known method for the synthesis of sulfur diamides ( A ) and sulfur diimides (B)[''. To
our knowledge, however, no sulfur derivatives of type (C)
have yet been prepared in this way[lbl.
We have now found that N,N-bis(trimethylstanny1)trifluoromethanesulfonamide[*I (I ) reacts with sulfur dichloride in
[*] Prof. Dr. H. W. Roesky, Dipl.-Cbem. M. Diehl
Anorganisch-chemisches Institut I der Universitat
Niederurseler Hang, D-6000 Frankfurt am Main 50 (Germany)
Prof. Dr. H. Fuess, Dr. J. W. Bats
Institut fur Kristallographie der Universitat
Senckenberganlage 30, D-6000 Frankfurt am Main 1 (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft
and the Bundesministerium fur Forschung und Technologie.
58
1 1 82
Fig. 1. Molecular structure and numbering of the atoms of (3); bond lengths
in A.
In the case of the shortest SN bond (S2-N2: 155pm)
sulfur has coordination 4 and nitrogen coordination 2. An
increase in CN of the atom N1 leads to a lengthening of
the S3-N1 distance to 161pm. A similar effect is observed
for the sulfur atom S1 having CN 3. SI-N2 is shorter than
S1-N1. According to structural studies performed so far
on sulfilimines and ~ulfarnates[~'
this observation could be
of general validity for sulfur having coordination numbers
4 and 3, leading to the following series of increasing bond
lengths :
S(CN=4)-N(CN=2) < S(CN=4)-N(CN=3) %
S(CN = 3)-N(CN= 2) < S(CN = 3)-N(CN = 3)
On the other hand, the tin atom is in a trigonal-bipyramidal
c~nfiguration[~]
in the crystal, with the three methyl groups,
Angew. Chem. Int. Ed. Engl. 17 (1978) No. 1
the N1 atom, and the 0 3 atom of an adjacent molecule
as nearest neighbod5I.
Experimental
A solution of SC12 (1.03g, 0.01 mol) in CH2C12 (20ml) is
slowly added dropwise to a stirred suspension of (1) (4.77g,
0.01 mol) in CH2Cl2 (30ml). The red color of SC12 disappears,
and a clear solution is formed. Compound ( 2 ) is precipitated
as intermediate, and is consumed on further addition of SCI2.
A clear solution is formed once again. On completion of
the reaction (ca. 3 h) compound ( 3 ) precipitates; recrystallization from CH2C12 gives colorless needles, m.p. 132--134°C.
After removal of solvent and sublimation of (CH3)3SnCland
(CH3)2SnC12in an oil-pump vacuum at 40°C most of the
product is obtained as residue; yield 0.5 g.-IR (Nujol, cm- '):
1380s, 1340s, 1335m, 1242s, 1235s, 1225s, 1216s, 1205s,
1194s, 1152s, 1038m, 1005w,981 m,917 s,795 m, 770m, 767 w,
738 w.-MS(70eV): m/e(rel. int.)= 506 M + (I),491 M + - CH3
(59), 165 (CH3)3Sn (100).-19F-NMR: 6 = -77.8 (s).-'HNMR: G(CH3)3Sn=-0.96 (s), 6(CH3)= -2.9 (s),
Received: November 17, 1977 [Z 877 IE]
German version: Angew. Chem. 90,73 (1978)
CAS Registry numbers:
( I ) , 65149-87-3; ( 2 ) , 65149-88-4; ( 3 ) , 65167-96-6; SCI2, 10545-99-0
[I] a) U . Wannagat, H . Kuckertz, Angew. Chem. 74.11 7 (1962); Angew. Chem.
Int. Ed. Engl. 1 , 113 (1962); 0. J . Scherer, Organomet. Chem. Rev.
A 3 , 281 (1968); b) cf. however, D. Hanssgen, W Roefle, J. Organomet.
Chem. 63,269 (1973).
121 H . W Roesky, M . Diehl, M . Banek, Chem. Ber., in press.
[3] A. Kdlmdn, Acta Crystallogr. 22, 501 (1967); A. Kdlmdn, B. Dufln, A.
Kucsman, ibid. B27, 586 (1971); A. Kdlmdn, K . Sasuciri, A. Kucsman,
ibid. B29, 1241 (1973); G. W Cox, 7: M . Sabine, !l M . Padmanabhan,
N . Tu Ban, M . K . Chung, A. J . Surjadi, ibid. 23, 578 (1968).
141 H . W Roesky, G. Holtschneider, H . Wiezer, B. Krebs, Chem. Ber. 109,
1358 (1976).
151 J . W Bats, H . Fuess, M . Diehl, H . W Roesky, Inorg. Chem., in press.
The First Reversible Thermal Dissociation of
Distannanes, R3Sn-SnR3
By Hans U . Buschhaus and Wilhelm P. Neumannp]
Hexaalkyldistannanes have hitherto been considered as
thermally stable up to at least 170°Cr'1 or even 235"Cr2].
At higher temperatures irreversible formation of alkyl radicals
and polymers, and deposition of tin were observed. As with
highly substituted ethanes and their reversible dissociation
to a l k ~ l [or
~ ] ketyl radicals[4], the' frontstrain or backstrain
of bulky residues should also weaken the Sn-Sn bond to
such an extent that reversible thermal dissociation may occur.
We have now been able to observe this effect in the case
of the aryl derivatives (1 ) ;
R3Sn--SnR3*
(1)
A
disappear instantaneously upon cooling (g = 2.0075, line width
5 G). The more bulky ethyl group in (1 b ) is seen to have
a considerable influence. ESR intensity measurements gave
the dissociation energies DsnPSn=190+8 kJ/mol for (1 a ) ,
and only 125f5 kJ/mol for (1 b ) , which is considerably less
than for Me3Sn-SnMe3 (210-240 k J / m ~ l ) [ ~ ] :
We have prepared the previously unknown djstannanes
(1) by a novel procedure:
2R3SnH +NC-CMe2--N=N-CMe2-CN&
(3)
During this reaction, carried out in nonane at lOO"C, the
ESR signals of the stannyl radicals ( 2 ) appear.
Thus, two further transient radicals R3Sn. have become
accessible to measurement in solution, in addition to the tris(2-phenyl-2-methylpropy1)stannylradical which was recently
subjected to detailed study as an example of this speciesi6].
Procedure
Preparation of ( l a ) : (3a)['](2.5 g, 3.1 mmol) is dissolved in
anhydrous toluene (50ml) in an argon atmosphere. Azoisobutyronitrile (0.37 g, 2.2 mmol) is then added, and the mixture
is stirred for 8 h at 60°C. A colorless solid is deposited, which
is filtered off with exclusion of air, washed twice with hot
toluene, and dried in vacuo. Yield: 1.3g(87 %)of (1 a ) , colorless
crystals, dec. >3OO"C, identified by CH analysis, IR, mass
spectrometry, very sparingly soluble in the usual solvents,
sparingly soluble in phenanthrene or 1-methylnaphthalene.
( l b ) is prepared similarly from (3b) (5.0 g, 8.3 mmol), obtained by a procedure resembling that for (3a), in nonane (50
ml) and azoisobutyronitrile (1.40 g, 8.3 mmol). After centrifugation and recrystallization from nonane, colorless needles are
isolated, dec. >300"C, soluble in hot nonane and l-methylnaphthalene, identified by CH analysis, IR, and mass spectrometry.
Dissociation experiments: In an ESR tube, (1 a ) (about
50mg) is suspended in I-methylnaphthalene (1 ml) or melted
in phenanthrene (3 g) under argon, or (1 b ) (50mg) is suspended
in 1-methylnaphthalene (1 ml) or nonane (1ml), and heated
tothedesired temperaturein a Varian E6 X-band ESR spectrometer. Intensity measurements are performed on ( 2 a ) in the
180-230°C range (at higher temperatures ( l a ) becomes red
and decomposes irreversibly), and on (2b) in the 100160°C range. The intensities of the signals depend on the
applied microwave energy. UV irradiation of ( 1 a) and (1 b )
yields ( 2 a ) and ( 2 b), respectively, even at lower temperatures.
Received: October 10, 1977
supplemented: November 3, 1977
German version: Angew. Chem. 90.74 (1978)
CAS Registry numbers:
( l a ) , 65015-62-5; ( l b ) , 65015-63-6; ( 2 0 ) . 65015-64-7; ( 2 6 ) - 65015-65-8;
( 3 a ) , 56797-46-7; ( 3 6 ) , 65015-66-9
[l]
2R3Sn.
(2)
( a ) : R=2,4,6-trimethylphenyI
( b ) : R =2,4,6-triethylphenyl
121
131
Equal ESR singlets begin to appear in solutions of ( l a )
at 180"C, and even at 100°C in solutions of ( l b ) . They
[*I
141
[5]
[6]
Prof. Dr. W. P. Neumann, Dipl.-Chem. H. U. Buschhaus
Lehrstuhl f i r Organische Chemie I der Universitat
Otto-Hahn-Strasse, D-4600 Dortmund 50 (Germany)
Angew. Chem. Int. Ed. Engl. 17 ( 1 9 7 8 ) No. 1
N2+2HCMe2-CN+(l)
[7]
W P . Neumann, E. Petersen, R . Sommer, Angew. Chem. 77, 622 (1965);
Angew. Chem. Int. Ed. Engl. 4, 599 (1965).
E . J . Bulton, H . A. Budding, J . G. Noltes, J. Organomet. Chem. 22,
C 5 ( 1 970).
K . Ziegler, Angew. Chem. 61,168 (1949); H . D. Beckhaus, Ch. Riichardt,
Chem. Ber. 110, 878 (1977); further references given therein.
W P. Neumann, B. Schroeder, M. Ziebarth, Justus Liebigs Ann. Chem.
1975, 2279; further references given therein.
Review: 19: P . Neumann: The Organic Chemistry of Tin. Wiley, London
1970, p. 9.
H . U . Buschhaus, M . Lehnig, W P . Neumann, J. Chem. SOC. Chem.
Comm. 1977, 129.
D. H . Lorenz, P . Shapiro, A. Stern, E. 1. Becker, J. Org. Chem. 28,
2332 (1963).
59
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bond, чrelation, length, amid, coordination, imide, number, methanesulfinamidine, alkylsulfur
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