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As4S5N10ЦA Diaminosulfane Derivative with Two Bicyclic Arsino Sulfur Diimides.

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(OS(CO)~CI(
PHPh)( PPhJ2]
[W(=CCMe3)Cl2(PHPh)(PEt,),]
3
4
As&N,,-A
Diaminosulfane Derivative with Two
Bicyclic Arsino Sulfur Diimides""
The synthetic utility of magnesium phosphido reagents
in gaining access to other metal phosphido complexes is
being investigated. Interestingly, reaction of 5 with 1 gave
the known diphosphene complex 6"" rather than the expected phosphido
[NiCl2I(PR2CH2)d+ IMg(PHPh)21
5
-
1
[Ni(q-Ph- P= P-Ph)(( PR,CH,)&
6
Received: July 28, 1986;
revised: November 3, 1986 [Z 1879 IE]
German version: Angew. Chem. 99 (1987) 61
By Max Herberhold,* Karlheinz Guldner, Arfred Gieren,
Catalina Ruiz-PPrez. and Thomas Hiibner
The reaction of the salt K2SNz with organoarsenic chlorides has proved useful for the synthesis of the arsenicsubstituted sulfur diimides 1 and 2.".21According to the
X-ray structure analysis of 1 ( R = Ph), the sulfur diimide
skeleton in the bis(diorganoarsin0) sulfur diimides 1 has
the Z / Z
the eight-membered ring in 2
(R=tBu) has the boat form.[*] Compounds of type 1 were
first described in 1984;1'1eight-membered ring compounds
of type 2 with R=Me,l3l Ph,I4] and MesL4Ihad been obtained previously.
KS
, N,
+2
R2AsCL
CH3CN
- 2
KCI
>
R,i
R,As
/+
N
I ,R
ASlR
1
R = Me, tBu, cyclo-C6H,,. Ph
[I1
W. E. Lindsell in G. Wilkinson, F. G. A. Stone, E. W. Abel (Eds.): Comprehensive Organometallic Chemrsfry, Vol. I . Pergamon Press, Oxford
1982, p. 155; M. S. Vharasch, 0. Reinmuth: Grignard Reactions ofNonmerallic Substances. Constable, London 1954.
[2] A. Job, G. Dussolier, C. R. Hebd. Seances Acad. Sci. 184 (1927) 1454;
Chem. Absfr. 21 (1927) 3049; F. G. Mann, 1. T. Millar, J. Chem. SOC.
1952, 3039; K . Issleib, C. Rock Stuoh, 1. Duchek, E. Fluck, Z. Anorg.
Allg. Chem. 360 (1968) 77.
[3] K. Issleib, H. J . Deylig, Chem. Ber. 97 (1964) 946.
[4] Experimental procedure for 1 (exclusion of air and water): To PhPHI
(3.03 g, 27.5 mmol) in pentane (30 mL) was added a 0.7 M solution of
nBusBuMg in heptane (88 mL, 61.6 mmol). In an exothermic reaction a
white precipitate formed. The solution was then stirred at 25°C for 2 h.
The product (6.34 g, 95%) was collected, washed with pentane, and dried
in vacuo. I is pyrophoric, insoluble in pentane, hexane, and toluene,
and soluble in donor solvents. 1R: v(P-H)=2280 (w). v(Mg-P)=510300 cm - ' (br, structured).
[ 5 ] Experimental Procedure for 2 : 1 (2.03 g, 8.37 mmol) was dissolved in
TMEDA (4 mL). The resulting pale yellow solution was stirred for I h at
25"C, then pumped dry. The product was recrystallized from toluene/
pentane. Yield: 2.33 g (78%); white crystals, m.p.= IIS-12O"C (dec.).
'H-NMR (C6D,, 25% TMS): 6=7.66-6.97 (m, Ph), 5.05, 2.57 (d, J ( ' H "P)= 198.6 Hz, P-H), 1.94 (s, CH,), 1.86 ( s , CHZ). "P-NMR (CaD,,
2 5 T , 85% H3P04): 6 ( ' H decoupled)= - 123.64 (s), 6 ( ' H coupled)= - 123.65 (I), - 123.70 (1. J("P-'H)= 198.5 Hz). IR: v(P-H)=
2262 (m), 2250 (m) cm - I _
[6] J. J. Eisch, R. Sanchez, J. Organomet. Chem. 296 (1985) C 2 7 ; A. W.
Duff, P. B. Hutchcock, M. F. Lappert, R. G. Taylor, ibid. 293 (1985) 271 ;
M. Henderson, R. 1. Papasergio, C. L. Raston, A. H. White, M. F. Lappert, J. Chem. SOC.Chem. Commun. 1986, 672.
171 R. Benn, H. Lehmkuhl, K. Mehler, A. Rufinska, Angew. Chem. 96 (1984)
521; Angew. Chem. Int. Ed. Engl. 23 (1984) 534.
[S] 2, triclinic, PT(C;, No. 2), a = 11.916(6), b= 11.612(7), c=9.080(6) A,
a=68.42(4),P=85.11(5), y=62.39(4)', V = 1030(1)
Z=2,pC,,,,= l.l>
g.cm-3, F(000)=384, monochromatic MoKa radiation, A=0.71079 A,
pM,,=2.5 c m - I, specimen size ~ 0 . mm
2 (capillary); Syntex-Pi diffractometer, =2O"C, 28,.,,=45", 2024 reflections, 1276 with 1 > 2 o ( I ) , direct methods, full matrix refinement, R. R'= 0.076, 0.057 (statistical
weights). Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Energie, Physik, Mathematik
GmbH, D-7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository number CSD-52260, the names of the authors, and the journal
citation.
[9] H. G. von Schnering, 0. Menge, 2. Anorg. Allg. Chem. 422 (1976) 219.
[lo) D. S . Bohle, T. C. Jones, C. E. T. Richard, W. R. Roper, J. Chem. Soc.
Chem. Commun. 1984, 865.
[ 1 I] S . M. Rocklage, R. R. Schrock, M. R. Churchill, H. J. Wasserman, Orgonometalhcs I (1982) 1332.
I121 D. S . Bohle, W. R. Roper, J . Organomet. Chem. 273 (1984) C7.
[I31 H. Schafer, D. Binder, D. Fenske, Angew. Chem. 97 (1985) 523; Angew.
Chem. I n / . Ed. Engl. 24 (1985) 522.
[ 141 Experimen/alprocedure for 6 : 5 (0.23 g, 0.42 mmol) was allowed to react
with I (0.10 g, 0.41 mmol) in 20 mL of tetrahydrofuran at ca. 20°C.
Cooling of the mixture to ca -30°C afforded green crystals of 6 I131
(0. I 5 g, 53% yield), which were washed with hexane and dried in vacuo.
Surprisingly, the corresponding reaction of K2SN2with
arsenic halides AsX, (X=Cl, Br, I) does not lead to the
expected cage compound As(NSN)~AS,even though the
analogous silicon compound, MeSi(NSN)3SiMe,'51 is
known. Instead, 3 is formed preferentially in the course of
a redox reaction.
Starting from AsBr,, compound 3 is obtained in about
40% yield as red, moderately air-stable crystals, which are
poorly soluble in hydrocarbons and diethyl ether, moderately soluble in acetonitrile, and very soluble in dichloro-
\
A',
82
0 VCH Verlagsgesellschaji mhH. 0-6940 Wernherm. 1987
.
R = fBu
3
[*] Prof. Dr. M. Herberhold, Dr. K. Guldner
Laboratorium fur Anorganische Chemie der Universitat
Universitatsstrasse 30, D-8580 Bayreuth (FRG)
Prof. Dr. A. Gieren ['I. DipLPhys. C. Ruiz-Perez, Dr. T. Hubner
Max-Planck-Institut fur Biochemie
D-8033 Martinsried (FRG)
['I Present address:
lnstitut fur Anorganische und Analytische Chemie der Universitat
Innrain 52a, A-6020 lnnsbruck (Austria)
[**I This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
0570-0833/87/0101-0082 $ 02.JO/O
Angew Chem. Int Ed. Engl. 26 11987) No I
methane. In the mass spectrum, the peaks for the molecular ion As,S,N:?
(m/z 600) and for As2SN': (m/z 224) are
very intense. In the I R spectrum, the two bands at 11431
1119 (vs) can be tentatively assigned to the v,,(NSN)
stretching mode, and the bands at 1069/1039 (s) to the
v,(NSN) stretching mode of the sulfur diimide units in the
bicyclic moieties.
N22
m
N42
(w), 805 (w), 722 (w). 662 (s), 632 (m). 590 (s), 495 (vs), 470 (sh), 457 (s), 410
(s), 391 (w).
Received: September 12, 1986;
revised: October 21, 1986 [Z 1927 IE]
German version: Angew. Chem. 99 (1987) 81
[I] M. Herberhold, W. Ehrenreich, K. Guldner, Chem. Ber. 117 (1984)
1999.
[2] A. Gieren, H. Betz, T. Hiibner, V. Lamm, M. Herberhold, K. Guldner, Z.
Anorg. Allg. Cbem. 513 (1984) 160.
131 0. J. Scherer, R. Wies, Angew. Chem. 83 (1971) 882: Angew. Chem. In[.
Ed. Engl. 10 (1971) 812.
[4] N. W. Alcock, E. M. Holt, J. Kuyper, J. J. Mayerle, G. B. Street, fnorg.
Chem. 18 (1979) 2235.
[5] H. W. Roesky, M. Witt, B. Krebs, G. Henkel, H.-J. Korte, Chem. Ber.
114 (1981) 201.
[6] M. Herberhold, W. Ehrenreich, Angew. Cbem. 94 (1982) 637; Angew.
Chem. I n [ . Ed. Engl. 21 (1982) 633; Angew. Chem. Suppl. 1982. 1346.
[7] X-ray structure analysis of 3.0.5CH2CIZ: monoclinic, space group C2/
c, a= 16.523(4), b = 16.790(3), c= I1.458(3)
,8=97.03(2)", Z = 8 ,
P.:,,.~ =2.528 g cm-', p,,,,=2.525 g cm-'. CAD4, MoKllrgraphite monochromator, 2761 unique reflections observed (1>2o(I), 1.5"58528"),
Patterson, Fourier, difference Fourier syntheses. R =0.038 ( R , =0.041;
w=k/(u2(1FOI) 0.0003 lfiplz).C H L I Z in a special site at 2. Further details of the crystal structure investigation may be obtained from the
Fachinformationszentrum Energie, Physik. Mathematik GmbH, D-75 14
Eggenstein-Leopoldshafen2 (FRG), on quoting the depository number
CSD-52091, the names of the authors, and the journal citation.
[8] A. Gieren, T. Hiibner, M. Herberhold, K. Guldner, G. Suss-Fink, Z
Anorg. Allg. Chem. (1986). in press.
[9] A. Gieren, B. Dederer, Z. Anorg. Allg. Chem. 467 (1980) 68.
[lo] V. Lamm, M. Rabben, A. Gieren, 2. Anorg. Allg. Cbem. 507 (1983)
A,
N11
+
RS3
100.
Fig. I . Crystal structure of 3. a) Bond lengths [A] and angles ["I averaged
over mm2 symmetry. b) Diaminosulfane moiety projected onto N-S-N. c)
Projections in the directions Asl-As2 and As3-As4.
[ I l l H. W. Roesky, W. Clegg, J. Schimkowiak, M. Schmidt, M. Witt, G. M.
Sheldrick, J. Chem. Soc. Dalton Trans. 1982. 21 17.
Imino-, Phosphoranylidene-, and
Sulfuranylidenephosphanes by
The structure of 3 (Fig. 1) was determined by X-ray
1,3-Silyl Migration**
structure analysis of 3 .0.5 CHzC12.[71A diaminosulfane
derivative is found in which two bicyclic [As2S2N,] units
By Frank Zurmuhlen and Manfred Regitz*
are coupled through a sulfur atom. In both the entire molCompounds containing h' phosphorus with coordinaecule and the two cages, the highest possible symmetry
tion number 2, such as methylenephosphanes ("phosmm2 is reduced to 2. However, even this symmetry is not
phaalkenes") 1
iminophosphanes 2,"l and phosphanstrictly imposed. The structure of the AS(NSN)~ASeightylidenephosphanes ("diphosphenes") 3p1play an impormembered rings is comparable to that in compounds of the
tant role in current developments in phosphorus chemistry.
type 212.41
and in [Os3(CO),o(p-(tBu)As(NSN)2As(tBu)}].181
We describe here the preparation of low-coordinate phosThe N = S = N groups have the geometry characteristic of
phorus compounds of types 2, 4, and 5 from silylated
sulfur diimides"] (S=N bonds: 1.522 A) and are nearly cophosphides and acid chlorides, the P/X double bond beplanar with theodirectly bonded As atoms. The As. . .As
ing introduced by 1,3-silyl m i g r a t i ~ n . ~ ~ ]
distance (3.295 A) in 3 is significantly smaller than that in
comparable c ~ m p ~ u n d s ~ and
' . ~ . even
~ ] shorter than that in
/
/
/
/
1 ( R = Ph) (3.379 A).['] The shorter As. . .As distance is ac-P=C
-P=N
-P=P
'p=p I
-P=S
\
\
\
companied by a reduction of the As-N=S, N-As-N, and
1
2
3
4
5
N=S= N angles in the eight-membered rings. The diaminosulfane moiety As2N-S-NAsz has the geometry[".' 'I characteristic of this structural unit with the lone pairs of elecIminophosphanes 2 are known[31 (albeit without the
trons on the N atoms in the N-S-N plane; the N atoms are
= N O R structural unit); phosphoranylidenephosphanes 4
situated 0.16(2) A (N51) and 0.32(3) A (N52) outside of the
are largely uninvestigated;161 sulfuranylidenephosphanes
plane of their three binding partners ("transoid arrangewere u p to now completely unknown.
ment of electron pairs"["I); the S-N bonds (1.680 A) are
The reaction of nitrosyl chloride 7a with the lithium
somewhat shorter than a S-N single bond.
phosphide 6al7]in pentane at - 50°C affords, after distillative workup (200°C, kugelrohr) the thermally extremely
stable
iminophosphane 9a ; the conceivable dimerization
Experimental Procedure
A suspension of K2SN2 (0.58 g, 4.2 mmol) [6] in acetonitrile (100 mL) was
allowed to react at -40°C with a solution of AsBrl (0.88 g, 2.8 mmol) in
ether (20 mL). After thawing, the orange-brown mixture was stirred for 2 h,
filtered through Na2S0, (anhydrous), concentrated to half of the original
volume, and cooled to -30°C. The crude product 3 separated out as an
orange-red powder (0.17 g, 40%). which can be recrystallized from CH2C12o r
ether/CH?CI2 ( 5 1 I). Red crystals (3 .0.5CH2C12),dec. above 138°C. IR (Nujol): GIcm- ' ] = I143 (vs), I I19 (vs), 1069 (s), 1039 (s), 1027 (vs), 966 (w), 912
Angew Chem In1 Ed. Engl. 26 (1987) No. I
1'1 Prof. Dr. M. Regitz, DipLChem. F. Zurmiihlen
[**I
Fachbereich Chemie der Universitat
Erwin-Schrodinger-Strasse,D-6750 Kaiserslautern (FRG)
Phosphorus Compounds with Unusual Coordination, Part 14. This work
was supported by the Fonds der Chemischen Industrie and the Landesregierung of Rheinland-Pfalz.-Part 13: R. Hussong, H. Heydt, M. Regitz, Z. Naturjorsch. 8 4 1 (1986) 915.
0 V C H Verlagsgesel~schaftm b H . 0-6940 Weinheim. 1987
0570-0833/87/0101-0083 $ 02.50/0
83
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two, bicyclic, diimides, sulfur, arsino, as4s5n10цa, derivatives, diaminosulfane
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