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The synthesis of [Ph4As+]2[Cl4Re(NS)(NSCl)2-] · CH2Cl2 (4) from the reaction of S4N4, Cl4ReN, and Ph4AsCl is reported. CH2Cl2 is used as solvent. The reaction of S4N4 with Re2Cl10 similarly leads to the salt [Ph4As+][Cl2ReNS-] (5) in a smaller yield. 4 crystallizes in the triclinic space group P1̅ with Z = 2, a - 10.434(2), b = 12.1454(6), c = 21.125(2) Å, a = 81.210(6), β = 86.70(1), γ = 76.624(8)°.
Über Reaktionen von 3-trifluormethylphenylsubstituierten silicium-und zinnorganischen Verbindungen
(1978)
Several routes were investigated for the preparation of 3-CF3C6H4N[Si(CH3)3]2 2 and 3-CF3C6H4N[Sn(CH3)3]2 3. The latter compound reacts with 3-CF3C6H4NCO to yield [3-CF3C6H4(CH3)3SnN]2CO 4. A substituted urea 5 is also formed from [(CH3)3Si]2NCH3 and 3-CF3C6H4NCO. 5 is used for the preparation of cyclic compounds, with S2Cl2 the ten-membered ring (3-CF3C6H4NCONCH3S2)2 6 is formed. 5 and HN(SO2Cl)2 yield the six-membered ring 3-CF3C6H4NCONCH3(SO2)2NH 7. SeOCl2 and 5 react under formation of a spiro compound (S-CF3C6H4NCONCH3)2Se 8. The compounds were characterized on the basis of mass and 19F NMR spectra.
N-Sulfonylsulfimide
(1978)
(CF3SO2NSO2)2 (1), a compound with a four-membered ring, was prepared from CF3SO2NSO and SO3. 1 as well as (FSO2NSO2)2 form 1:1 adducts with S4N4 , pyridine and pyridine carbonitrile-4 (2a-2f). By comparison with FSO2NCOS4N4 it was shown that a dipolar type of addition had occured. In contrast the reaction of 1 and (FSO2NSO2)2 with aromatic nitriles yields 1:2 cycloaddition products (3a-3g) which were characterized on the basis of mass spectra. The six-membered rings of 4a-4b which contain carbon, nitrogen and sulfur atoms were obtained from the reaction of isocyanates with (FSO2NSO2)2 or (CF3SO2NSO2)2. 4-BrC6H4NCO and SO3 react in a similar way to yield 5. The starting materials are extremely sensitive to moisture while most of the adducts can be handled in open air without decomposition.
The kinetically stable triazatriphosphorinyl and tetraazatetra-phosphorocinyl azides 3 and 4 are prepared from the corresponding chlorides 1, 2 with sodium azide. 3 and 4 react with phosphanes to yield the λ5 -diphosphazenes 5a-d. By the reaction of 1 or 2 with KCN the nitriles 6 and 7 are formed. -The new compounds are characterized on the basis of IR and mass spectra.
The title compound N,N-bis(trimethylstannyl)trifluoromethanesulfonamide (1) reacts with S2Cl2, SOCl2 and SO2Cl2 in a molar ratio 2:1 to yield the compounds S2Cl2 a twelve-membered ring 6. These are the largest neutral sulfur-nitrogen rings of coordination number two at the sulfur atoms known to date. 3 reacts with SOCI2 under migration of a methyl group from the tin to a sulfur atom to yield CF3SO2(R3Sn)NS(CH3)NSO2CF3 (7). 2,2,4,4-Tetramethyl-1,3-bis(trifluormethylsulfonyl)cyclodisilazan and 7 are formed by the reaction of 3 with R2SiCl2- The analogous four-membered germanium compound 8 is obtained from 1 and R2GeCl2. While the pyrolysis of 1 yields only the six-membered cyclotristannazan 9, the six-membered germanium analog is only formed in minor amounts. By treating 9 with R3SiCl the ring is decomposed to give 10. A six-membered ring is formed from the reaction of 1 with ClR2SiOSiR2Cl 11. The structure of 6 is discussed in detail. 6 crystallizes in the monoclinic space group C2/c with a = 24.408(5), b = 7.377(2), c = 16.715(3) Å, β = 117.16(3)° and Z = 4. It has a chair conformation which is different from the isoelectronic S12-structure.
S4N3Cl reacts with sulfonic acids and imido- bissulfonyl derivatives under HCl-evolution to the following compounds: S4N3SO3CF3, S4N3N (SO2F)2, S4NSO3CH3HSO3CH3, S4N3N (SO2CF3) SO2Cl and S4N3N (SO2CF3) SO2F, They are yellow solids which decompose when heated below the melting point. The compounds are formed in nearly quantitative yield and have been characterized by elemental analysis, nmr and electronic spectra.
The preparation of (CH3)3SnSPSFC2H5, Pb(SPSFCH3)2, Pb(SPSFC2H5)2 and CH3HgSPSFCH3 is described. On the basis of NMR the structure was formulated as ... All the complexes are colourless and monomeric in solution. The magnetic and reflectance spectra of Cr(S2PFCH3)3, Mn(S2PFC2H5)2, Co(S2PFCH3)2, Ni(S2PFCH3)2 and Ni(S2PFC2H5)2 are reported and interpreted.
By substitution of a halogen atom in cyclic phosphazenes by isocyanate or isothiocyanate new members of this class of compounds are synthesized. These compounds are fairly stable against hydrolysis. Reaction of the new compounds with amines yields
P3N3F5NHC(O)N(CH3)2 and P3N3F5NHC(S)N(CH3)2. With elemental chlorine P3N3F5N = CCl2 is formed. Numerous IR, NMR and mass spectra data of the new compounds are reported.
P3N3F5NHNH2 reacts with P3N3F5Br to yield the symmetric hydrazide P3N3F5-NHNHP3N3F5. Compounds of the type P3N3F5NHNHC(O)CX3 and P3N3F5NHN = CX2 are readily prepared from P3N3F5NHNH2 and carbonic acid chlorides and respectively aldehydes and ketones.
The reaction product of P3N3F5NHNH2 and CH3CH2CHO gives a dimeric derivate. Its structure was proofed by molecular weight, IR- and mass spectra.