Jiří Toužín

New Heterocyclic Organophosphorus-Sulfur-Nitrogen Compounds, Syntheses and Structures.

The new compound C10H6P(S)[NSi(CH3)3]2P(S) (3) which contains a P2N2 heterocycle has been prepared in an 8% yield by partial thermal decomposition of 1-{[N,N-bis(trimethylsilyl)acetamidinium]sulfido}-3-(trimethyls ilylamino)-1H,3H,1lambda5,3lambda5-naphth[1, 8a,8-cd][1,2,6]thiadiphosphinine-1,3-dithione [CH3C{NHSi(CH3)3}2]+ [C10H6P(S)(NHSiMe3) SP(S)2] (2). Reaction of 2 with potassium hydroxide in acetonitrile gives the completely desilylated product [CH3C(NH2)2]+ [C10H6P(S)(NH2)SP(S)2] (4). The structures of the new compounds 3 and 4 were elucidated by FTIR and nmr spectroscopic methods and by x-ray structure analyses.

Reaction of Naphthalenedithiadiphosphetanedisulphide with Ethylene Glycol

Reaction of the title compounds (molar ratio 1:30) in refluxing toluene results in cleavage of one of the P-S-P bridges in naphthalenedithiadiphosphetanedisulphide 1 and formation of a new heterocycle 2 which contains a C3P2S ring with the phosphorus atoms substituted by OCH2CH2OH groups; reaction at 140°C results in complete desulphuration of napthalenedithiadiphosphetanedisulphide 1 and formation of the new heterocycle 1,8-naphthodiphosphonic acid anhydride 3 which contains a C3P2O ring. 2 and 3 were characterised by microanalysis, IR, 31P NMR and X-ray crystallography: 2, monoclinic, space group C2/c with a = 17.564 (4), b = 12.475 (2) and C = 16.423 (3) A, β = 102.98 (3·), calculated density 1.54 g/cm3, Z = 8, reflections collected 1089, final R value 0.0501; 3, monoclinic, space group P21/c with a = 7.961 (2), b = 8.275 (2) and c = 16.192 (5) A, β = 96.93 (3), calculated density 1.694 g/cm3, Z = 4, reflections collected 1837, final R value 0.044. No reaction occurred when 3 was heated with H2O.

Reaction of Triselenium Heptoxide with Pyridine – Novel DA-complex 4Py· Se2O5

Se3O7 reacts with an excess of pyridine (Py) and forms the donor-acceptor (DA) complexes Py · SeO2 and 4Py · Se2O5. The latter compound was characterised by elemental analysis, Raman spectroscopy, thermal analysis and X-ray crystallography: orthorhombic system, space group Pbca with a = 17.133(5) A, b = 11.585(6) A c = 22.461(6) A, calculated density 1.652 g.cm−3, Z = 8, reflections collected, 2569, final R value 0.0442. This is the first compound in which tetravalent selenium atom is co-ordinated by three nitrogen atoms.