We assume the PH2F; cation to have a tetrahedral skel- etal structure (C2" point group). The nine normal vibra- tions are classified as 4A, + A2 + 2B, + 2Bz. Apart from the torsional vibration v5(A2), which is only Raman-active, all other vibrations should appear in both the IR as well as the Raman spectrum. The bands of the antisymmetric (v6) and symmetric (v,)PHI valence vibrations at 2600 and 2538 cm- ' , respectively, can be assigned by comparison with the valence vibrations of the isoelectronic compound SiH,F2[61; tentative assignment of the remaining bands [cm-'1: G(HPH) 1096 w, G(HPF) 1055 s, v,,(PF) 1010 s, v,(PF) 950 s, 6(HPF) 885 w, S(FPF) 835 s. Absorptions were observed at 695 and 645 cm- ' for the AsF, anion. NMR investigations have so far proved impossible, since no suitable solvent for ( I ) has yet been found.

Experimental

H,PF,['] (0.64 g, 7 mmol) and AsF5 (1.2 g, 7 mmol) are condensed together a t - 196°C in a metal apparatus. The mixture is allowed gradually to warm to room temperature and the volatile components are removed by suction, leav- ing behind 1.7 g (6.5 mmol) (93%) as crystalline, analyti- cally pure salt (1).

Received: March 13, 1981 [Z 909a IE] German version: Angew. Chem. 93. 1017 (1981)

CAS Registry numbers: ( I ) . 79593-53-6; H ~ F x , 13659-65-9; AsF,, 7784-36-3.

[ I ] R. D . Young in Kirk-Othmer: Encyclopedia of Chemical Technology, 3rd

[2] A. u. Bneyer, Liebigs Ann. Chem. 159, 269 (1870). 131 K. 0. Christe, J . P. Guertin, A. E. Paulath. Inorg. Nucl. Chem. Lett. 2. 83

(1966); W. E. Talberg, R. T. Rewick, R. S. Stringham. M . E. Hill, ibid. 2. 79 (1966); K. 0. Christe, W. W. Wilson, R. D. Wilson. Inorg. Chem. 19. 3254 (1980).

Ed., Vol. 2, Wiley-Interscience, New York 1978, p. 518.

(41 G. S. H. Chen. .I. Pussmore. J. Chem. SOC. Chem. Commun. 1973. 559. 151 K . 0. Christe, Inorg. Chem. 14. 2821 (1975). (61 S. Crndock, E. A. V. Ebsworth. A. G. Robiette. Trans. Faraday SOC. 60,

17) B. Blaser. K.-H. Worms. DBP 1 106736 (1962). I502 (1964).

Synthesis and Structure of a Non-Polymeric Molecule Containing Eleven Alternating Sulfur- and Nitrogen-Atoms[**] By Michael Witt, Herbert W. Roesky, Mathias Noltemeyer, William Clegg, Martin Schmidt, and George M. Shefdrick"' Dedicated to Professor Oskar GIemser on the occasion of his 70th birthday

We recently reported"] a ring contraction in the eight- membered ring S4N40, (I), which leads to the five-mem- bered ring system (2), a triphenylarsane adduct, in high yields.

I*] Prof. Dr. H. W. Roesky, M. Witt, Prof. Dr. G. M. Sheldrick, Dr. W. Clegg, Dr. M. Noltemeyer, M. Schmidt Anorganisch-chemisches Institut der Universitat Tammannstr. 4, D-3400 Gdttingen (Germany)

Fonds der Chemischen Industrie, and by Hoechst AG. [**I This work was supported by the Deutsche Forschungsgemeinschaft, the

(2) forms crystals (space group P2,/n) which are stable towards air and hydrolysis. We have now found that (2) slowly loses S4N4 and sulfur in acetone solution, and is converted into the condensation product (3).

This reaction can be explained mechanistically in terms of an intermediate formation of a dimer of (2) containing a central ten-membered ring system S6N4.

The molecular structure of (3) was determined by X-ray diffraction analysis on a single crystal[21. (3) proves to be the longest non-polymeric sulfur-nitrogen chain synthe- sized so far, with eleven alternating atoms. The compound cannot be sublimed without decomposition. The largest fragment appearing in the mass spectrum is (C6H5)3A~S at m / z = 338.

Fig. I . Structure of the molecule (3) in the crystal.

Bond lengths [A]: NI-SI 1.576(10), SI-N2 1.684(10), N2-S2 1.544(10), S2-N3 1.574(1 I), N3-S3 1.632(11), S3-N4 1.645(13), N G S 4 1.602(11), S k N 5 1.629(12), N5-SS 1.655(11), S5-N6 1.559 (1 1); NI-As1 1.756(12), N b A s 2 1.779(13), S-0 (mean value) 1.438(12), As-C (mean value) 1.892, C-C (mean value) 1.376 Bond angles I"]: Asl-NI-Sl 120.8(7), NI-SI-NZ 105.1(6), Sl-NZ-SZ

S3-N4-S4 l17.0(8), NGS4-NS 113.7(7), SGN5-SS 115.3(8), N5-SS-N6 104.3(6), SS-NbAsZ 118.9(9)

I l6.1(5), N2-S2-N3 110.4(6), S2-N3-S3 119.5(7), N3-S3-N4 96.3(6),

The S N bond lengths (and angles) in the two halves of the molecule of (3j differ considerably; the average S N bond length 1.602 A, however, is similar to the correspond- ing value of 1.611 in (SN).x'31. Nevertheless, shorter and longer S N bonds occur in (3) than in (SN), (1.593 and 1.628 A). The greater variation in the bond lengths in (3) appears to be a result of arbitrary folding of the molecule in the solid state.

Procedure

A solution of AsPh, (7.6 g, 25 mmol) in benzene (50 mL) is added dropwise to a solution of ( I ) (5.4 g, 25 mmol) in benzene (100 mL) and the mixture briefly heated to boil- ing. After cooling, the intense yellow precipitate is filtered off, dried, and extracted with acetonitrile. At room temper- ature, blood-red crystals of (2) precipitate out from the ex- tract. After filtration, the mother liquor is stored for a few

974 0 Verlag Chemie GmbH, 6940 Weinheirn. 1981 0570-0833/81/1111-0974 S 02.50/0 Angew. Chem. In[. Ed. Engl 20 (1981) No. I1

days in a refrigerator. A mixture of sulfur, S4N, and (3) separates out on the wall of the flask; after decanting off the solvent, the crystals of (3) can be separated manually from the mixture and recrystallized from CH,CN or ben- zene. (3) crystallizes from benzene with 3 molecules of sol- vation (m.p. 87"C, dec.), from CH3CN without any moie- cules of solvation (m.p. 146"C, dec.), as translucent orange needles.

Received: May 14, 1981 [Z 909b IE] German version: Angew. Chem. 93, 1017 (1981)

CAS Registry numbers: ( I ) . 57932-64-6; (2). 75768-56-8: (3). 79593-51-4; Asfh,, 603-35-0.

111 H. W. Roesky. M. Wiff. W. Clegg, W. Isenberg, M. Noltemeyer. G. M. Sheldrick. Angew. Chem. 92.959 (1980); Angew. Chem. Int. Ed. Engl. 19, 943 (1980).

121 Spacegroup P i , a = 10.987(4), b= 12.521(6), c=15.976(13) A,a=69.15(5), B= 80.66(5), y =73.69(4)0, Z = 2 ; four-circle diffractometer data,

[31 C. M. Mikulski. P. J . Russo, M. S. Saran, A. G. MacDiarmid, A . F. Garito, A. J . Heeger. J. Am. Chem. SOC. 97, 6358 (1975); C. M. Mikulski, M. S. Saran, J. Kleppinger, ibid. 98, 3844 (1976).

R = 6.2%.

Synthesis of Dithiophosphinato Complexes with Bis(diorganothiophosphory1)disulfanes: Mo&-Cluster Dithiophosphinates By Helmut Keck, Wilhelm Kuchen, Jiirgen Mathow, Beate Meyer, Dietrich Mootz, and Hartmut Wunderlich"'

Dithiophosphinate ions (I) reduce some metals accord- ing to eq. (a); simultaneously, they are themselves oxid- ized according to eq. (b) to bis(diorganothiophospho- ry1)disuifanes (2). Cu2+ reacts analogously to give R2PS2Cu. Presumably, dithiophosphinato chelates of the higher valence metal R,PS2M/m"l are formed as interme-

3 RzPS2- + Mmt -+ R2PS2M/n + R2P(S)-S2-P(S)R2 (a)

(1) ( ZU) , R = C 2H5

(Zh) , R = n-CSH?

e.g. M = Au, T1: m = 3, n = 1

diates. On the other hand, the disulfanes (2a) and (26) can oxidize metals according to reversed eq. (b), being them- selves reduced to chelate ligands (I). Thus, e.g. , on heating (2a) with c f (co)6 , tris(diethy1dithiophosphinato)chrom- i ~ m ( i i i ) [ ~ ~ l is formed according to

Cr(CO), + 3/2(2a) + (EtzPS2)3Cr + 6CO

Ni(C0)4 and Fe(CO)5 react analogously to give (Et2PS2)2Ni[2b1 and (Et2PS2)sFe[2b1, respectively; SnC12 is oxidized to (Et2PSz)rSnC1212cJ.

We have found that this reaction of the disulfanes can be used for the synthesis of Mo,S,-cluster chelates of type (3). and of dinuclear tungsten(v) complexes (4). On reac- tion with carbonyl complexes M(CO)6 of these metals they

['I Prof. Dr. W. Kuchen, Dr. H. Keck, Dipl.-Chem. J. Mathow, cand. rer. nat. B. Meyer, Prof. Dr. D. Mootz, Dr. H. Wunderlich Institut fur Anorganische Chemie und Strukturchemie der Universitat Universitatsstr. I , D-4000 Diisseldorf (Germany)

additionally act as sulfur transferring agents with conver- sion into monosulfanes R2P(S)-S-P(S)R2.

Thus, reaction of Mo(CO), with (Za) or (2b) affords the Mo"' compounds (3a) and (36). respectively:

IMoA(RzPS2)31 +[RzPS,I - (3a). R= Et, orange-red, decomp. above 260°C (3b), R=nPr, copper-red needles, decomp. above 200°C

The cluster structure of the 1 : 1 electrolytes (3a) follows from the elemental analysis, the "P( 'HI-NMR spectrum (6,= 110.1 and 73.5; intensity ratio 3 : I , saturated solution in CH2C12, relative t o 85% H,Po,), the field-desorption (FD) mass spectrum ([Mo,S,(Et,PS,),]+ m / z 977, ref. to 98Mo), and the X-ray structure analysis (Fig. 1). (36) exhi-

S

P \ -

Fig. I. Crystal Structure of the Mo'" cluster (3a) [6]. The orientation and as- signment of cation and anion are arbitrary. A disorder in the anion cannot be ruled out. (3a) crystallizes in two modifications with the lattice constants a=2065.1(3), b = 1015.2(2), c=1901.9(2) and a=2012.8(2), b=1565.5(2), c = l260.8( 1 ) pm, respectively. The corresponding orthorhombic space groups are Pca2, and Pnma, each with Z = 4 . The structure determina- tions with 2886 and 3414 significant measured diffraction intensities (o-scan, MoK,, 2&,, = 54") lead to R values of 0.058 and 0.045, respectively. In the latter case anion and cation have a crystallographic mirror plane. In both structures the Mo atoms form an equilateral triangle with an average bond length of 273.7 pm. Each of these bonds is bridged by a vertically oriented Sz-dumbbell on one side of the triangle, a single S atom trigonal-pyramidally coordinates the Mo triangle from the other side. This Mo,S7 cluster was first observed in Mo,S,CI, (4al. To each of the three Mo atoms a dithiophosphinato ligand is bonded via both S atoms. The two modifications differ in the con- formation of the organic moiety and in the arrangement of anions and ca- tions.

bits similar properties and a better solubility in many organic solvents. Reaction of (34 with triphenylphos- phane affords the sulfur-deficient chelate complex MO,S,(E~,PS~)~, a non-electrolyte, which forms deep- black, shiny crystals.

Molybdenum-sulfur clusters are of topical interest be- cause of their importance as model substances in bioinor- ganic chemistry'31. The method described here provides the first convenient access to Mo& clusters modified by or- gano groups[41. Thus, not only a high solubility in organic solvents is achieved, but the functionalization of these compounds by suitable choice of substituents R is also possible.

Reaction of W(CO), with (2) affords the tungsten com- plexes (4a, b).

We postulate a dinuclear structure for these non-electro- lytes. (4a): 'lP{ 'HI-NMR: 6,= 135.6 (saturated solution in 1,2-dichloroethane); electron-impact induced (EI) MS:

Angew Chem Inr Ed. Engl 20 (1981) No 11 0 Verlag Chemie GmbH, 6940 Weinheim. 1981 0570-0833/81/I111-0975 $02.50/0 975