The transition of the x-ally1 system to a dynamic ally1 system evidently is brought about by the strong electron donation to the nickel atom by two molecules of triethylphosphine. In x-C3H5PdCI, the same effect is achieved even with triphenyl- phosphine [31. Transitions of this type are produced thermally in Zr(C3H5)4 and Th(C3H5)4 [41.

Received: August 8th, 1966 [Z 308 IE] German version: Angew. Chem. 78, 941 (1966)

H2S i PH, DzS + PD, CHjSH + PHj

[l] G. Wilke and B. BogdanoviC, cited in G. Wilke et al., Angew. Chem. 78, 157 (1966), on p. 170; Angew. Chem. internat. Edit. 5, 151 (1966), on p. 163. [*] We thank Dr. E. G. Hoj'iiann for recording the 1H-NMR spectra. [2] I. E. Nordlander and J. D. Roberts, J. Amer. chem. SOC. 81, 1769 (1959). [3] J. Powell, S. D . Robinson, and B. L. Shaw, Chem. Commun. 1965, 78. [4] E. Steinriicke, Dissertation, Technische Hochschule Aachen, 1966; G. Wilke and E. Steinriicke, cited in G . Wilke et al., An- gew. Chem. 78, 157 (1966), on p. 162; Angew. Chem. internat. Edit. 5, 151 (1966), on p. 156.

HzPSH DzPSH HzPSCHj

Existence of Ternary Compounds of Phosphorus with Sulfur and Hydrogen

By Prof. P. W. Schenk and B. Leutner

Institut fur Anorganische und Analytische Chemie, Technische Universitat Berlin (Germany)

In this communication we report the first synthesis of volatile ternary compounds of phosphorus, sulfur, and hydrogen. Equimolar mixtures of gaseous H2S and PH3, or of D2S and PD3, or of CH3SH and PH3, were passed at 0.5 mmole/min and about 0.1 mm Hg through an electrodeless glow dis- charge (900 V at 90 mA and 27 MHz) [I]. The products were condensed at -196 OC; the conversion was 0.5-1.0 %. For analysis the gases were passed directly from the glow discharge into a small mass spectrometer [21 or condensed at -180 "C in a low-temperature infrared absorption cell. The following products were indentified:

Initial mixture I Main product I Subsidiary products

Mass-spectrometric identification of a product of molecular formula H3PS was complicated by the presence of H2S2 and P2H4 with the same nominal molecular weight (m/e = 66). The following evidence is proof for a compound H3PS: 1. The more frequent occurrence of a fragment of nominal mass 63 when a mixture of H2S and PH3 is subjected to a discharge than with pure P2H4; this indicates the presence of PS+ together with smaller amounts of P2H+. 2. The occurrence of the peak at m/e = 63 in the reaction products of PD3 + DzS, which can be due to PS+ only. 3. The formation of an analogous compound H2PSCH3 from CH3SH + PH3, the main peak of which at m/e = 80 is not overlapped by that of any other compound. A strong, sharp infrared band at 477 cm-1, which can be assigned to a P-S single bondr31, of the gas mixture con- densed at -180 "C supports the structure H2PSH. It follows from the decrease in intensity of this band that the colorless compound decomposes already above -130 'C to an amor- phous, nonvolatile, insoluble [41, yellow residue. The P: S ratio in this residue varies from 2: 1 to 6: 1 since, depending on the method of preparation, variable amounts of (also unstable) PzH4 and H2S2 are present.

H2PSCH3 is somewhat more stable. At -78 OC it still shows an infrared absorption with a P-S frequency of 480 cm-1; at this temperature, however, slow decomposition is notice- able from the spectrum. This compound also leaves a yellow, non-volatile residue.

Received: July 18th, 1966; revised August 4th, 1966 [Z 305 IE] German version: Angew. Chem. 78, 942 (1966)

[l] Telefunken high frequency generator HFG 120. [2] Quadrupole mass spectrometer AMP 3, Fried. Krupp, Me& und Analysentechnik, Bremen. [3] Such an IR band is observed, e.g., in the following compounds of known structure: P4S3; organophosphorus compounds [ R . A. Chittenden and L. C. Thomas, Spectrochim. Acta 20,1690 (1964)l. [4] Solvents: benzene, CS2, H2O; aqueous solutions of bases such as NaOH dissolve the residue by decomposition.

Di(cyc1ooctatetraene)titanium and Tri(cyc1ooctatetraene)dititanium 111

By Dr. H. Breil and Prof. G. Wilke

Max-Planck-Institut fur Kohlenforschung, Mulheim/Ruhr (Germany)

Di(cyclooctatetraene)titanium, Ti[COT]2 ( I ) , is obtained as deepviolet-red crystals in yields of over 80 % whenTi(OC4H9)4 is heated at 80 "C in the presence of an excess of cycloocta- tetraene (COT) and AI(C2H5)3 in the molar ratio 0.2:2:2. The compound is sparinglysoluble in aromatic hydrocarbons; the solutions are deep red. It can be recrystallized from hot toluene. Similarly, tri(cyclooctatetraene)dititanium, TiZ[COT]3 (2), is obtained as yellow crystals when the reactants are used in a molar ratio of 0.2:0.4:2 (yield 80 %). This complex is also sparingly soluble in aromatic hydrocarbons. Both compounds are extremely sensitive to air. They can he interconverted in accordance with the equation:

(C2H5)2A1H; 60 'C; 40 hr; 95 O/" f Ti2[COT]3 - Ti[COT]z -

COT; 80 "C; 40 hr, 94%

Ethanol reacts spontaneously with a suspension of (2) in CsH12 giving 1,3,5- and 1,3,6-cyclooctatrienes (88: 12), in 90 % yield, together with titanium ethoxide. Under the same conditions, ( I ) gives 1,3,5- and 1,3,6-cyclooctatrienes and cyclooctatetraene (51:37:12) in a total yield of 70 %. The complexes (1) and (2) react with formaldehyde or CO2 under pressure (ca. 50 atm) to form unsaturated hydroxy- methyl or carboxyl derivatives of unsaturated eight-mem- bered rings, which were converted in several steps into methyl- cyclooctanes. Mono-, di-, and trimethylcyclooctanes were obtained in every case; we also obtained these products analogously from methyl iodide and cyclooctatetraene- disodium. It must be conconcluded from the formation of mono-, di-, and trisubstituted derivatives of cyclooctane that transmetalation takes place during the reactions of both the titanium complexes and the cyclooctatetraenedisodium, and that the reaction does not occur exclusively in the 1,4-posi- tion, as described by Reppe et al. [21 for N a K O T ] . The chemical behavior of the cyclooctatetraene-titanium complexes indicated that the cyclooctatetraene molecules are bonded to the titanium atom at least partly as quasiaromatic, planar 10 x-electron systems, i.e. as dianions [31.

The "club sandwich" structure proposed for (2) has been confirmed in principle by X-ray analysis 141. The structure of ( I ) is not yet known. The presence of dianions is also indicated by the following synthesis:

CsH6.70 "C, 72hr, 53 Y, Tic14 + 2 Naz[COT] ~ _ _ _ - ---f Ti[COT]2+ 4 NaCl

898 Angew. Chem. internat. Edit. / Vol. 5 (1966) / No. 10