Trifluormethyl-schwefel-stickstoff-verbindungen. IX. Trifluormethansulfonamide

Trifluoromethanesulphonamide forms the following salts: CF₃SO₂NAg₂·NH₃, CF₃SO₂NAg₂, (CF₃SO₂NH)₂Hg and CF₃SO₂NH·NH₄. These salts are more reactive than the initial amide. CF₃SCl reacts with both silver salts to give the corresponding mono- and di-substituted derivatives, CF₃SO₂N(SCF₃)₂ and CF₃SO₂NHSCF₃, respectively. With phosgene and thiophosgene, CF₃SO₂NAg₂ reacts to give the pseudohalides CF₃SO₂NCO and CF₃SO₂NCS, respectively.     

Pseudochalkogenverbindungen. XXIV. Cyanamido-trimetaphosphimate

Pseudochalcogeno Compounds. XXIV. Cyanamido Trimetaphosphimates Synthesis and properties of sodium cyanamido trimetaphosphimates Na₃[P₃(NH)₃O_6?n(NCN)_n] (n:2,4) are reported. This compounds may be obtained by cautious hydrolysis of the corresponding hydrocyanamido-chloro-trimetaphosphimates, P₃N₃Cl_6?n(NHCN)_n. For sodium trimetaphosphimate, Na₃[P₃(NH)₃O₆] a simple, modified synthetic route is described. Possibilities of the formation of pseudochalcogeno-trimetaphosphimates of the type [P₃(NH) ₃O_6?n{C(CN)₂}_n]^3? (n = 2, 4) are discussed.     

Fluordiazadiphosphetidine, 5. Mitt.

Reaction of (CH₃NPF₃)₂ with equimolar amounts of N-methylhexamethyldisilazane yields a reaction product, which can be separated in a polymer and a crystalline fraction. High-vacuum sublimation of the crystalline part yields the already known compound (CH₃N)₄P₃F₇, the new spiro-isomer F₃P(CH₃N)₂PF(CH₃N)₂PF₃ and the spiro-compound F₃P(CH₃N)₂PF(CH₃N)₂PF(CH₃N)₂PF₃, an isomer of the known compound (CH₃N)₆P₄F₈.     

Anti-inflammatory drugs. X.

In the solid-state structure of the title compound, C₄H₁₀N⁺·C₁₄H₁₀Cl₂NO₂⁻·H₂O, the asymmetric unit contains one cation, one anion and a water mol­ecule. There is a network of hydrogen bonds which is similar to that found in the hydrated diethyl­ammonium diclofenac salt. A comparison is made of the molecular conformation of the anions in the two related structures.     

Cover Picture: Angew. Chem. Int. Ed. 7/2002

The cover picture shows Cu₂(μ‐O)₂ and Fe₂(μ‐O)₂ complexes with the M₂(μ‐O)₂ diamond core motif (the core is shown bottom right, M=green and oxygen=red spheres) and a representative example of a non‐heme multimetal enzyme (hydroxylase component of methane monooxygenase, in the background). Although quite a familiar feature in high‐valent manganese chemistry, the M₂(μ‐O)₂ diamond core motif has only recently been found in synthetic complexes for M=Cu or Fe. Despite differences in electronic structures that have been revealed through experimental and theoretical studies, Cu₂(μ‐O)₂ and Fe₂(μ‐O)₂ cores exhibit analogously covalent metal–oxo bonding, and similar tendencies to abstract hydrogen atoms from substrates. Our understanding of biocatalysis has been enhanced significantly through the isolation and comprehensive characterization of the Cu₂(μ‐O)₂ and Fe₂(μ‐O)₂ complexes. In particular, it has led to the development of new mechanistic notions about how non‐heme multimetal enzymes, such as, methane monooxygenase, fatty acid desaturase, and tyrosinase, may function in the activation of dioxygen to catalyze a diverse array of organic transformations. To find out more see the review by L. Que, Jr. and W. B. Tolman on p.1114 ff.     

Polysulfonylamines. CXXXII.

The crystal structure of the title compound, C₅H₇N₂⁺·C₁₂H₁₀NO₄S₂⁻, consists of two independent cation–anion pairs, A and B. Within each pair, the H—N—C—N*—H grouping (N*—H is the pyridinium function) and one N—S—O moiety of the anion are linked by N*—H⃛N and N—H⃛O hydrogen bonds to form an antidromic ring motif of type R²₂(8). The remaining amino donors give rise to N—H⃛O hydrogen bonds, connecting the ion pairs into A–B–A–B– chains. The structure testifies to the persistence of the R²₂(8) motif in question, which was previously detected as a highly robust supramolecular synthon in a series of onium di(methane­sulfonyl)­amidates. The structure is pseudosymmetric; the anion positions correspond to space group P2₁/n, but those of the cations do not.     

Hydrocarbon chemistry : by G.A. Olah (C. Eaborn). J. Organomet. Chem., 334 (1987) C49-C50.

Sequential displacement of both N₂ ligands from cis-[Mo(N₂)₂(PMe₂Ph)₄] by CNMe occurs by a dissociative (I_d) mechanism (k₂/k₁～5,k₁ 0.020 min^?1 at 273 K) via the intermediate cis-[Mo(N₂)(CNMe)(PMe)₂Ph)₄] For t-BuNC substitution, the only detected intermediate appears to be [Mo(CNBu-t)(PMe₂Ph)₄] and no intermediate was detected in reactions of trans-[Mo(N₂)₂(Ph₂PCH₂CH₂PPh₂)₂] with CNMe. N₂ appears to be labilised by cis-ligands in the order t-BuNC > CNMe > N₂ > NCR.     

Comments on the paper by Dr. C.A. McAuliffe

The first cyclopentadienylplutonium(IV) compounds, (η⁵-C₅H₅)₃PuCl and (η⁵-C₅H₅)₃Pu(NCS) have been prepared, the former by reaction of Cs₂PuCl₆ with TlC₅H₅ in CH₃CN and the latter by treating the chloride with KNCS in tetrahydrofuran. Both compounds are isostructural with ther U^IV and Np^IV analogues. The IR and UV/visible spectra of the new compounds are reported.     

Azole. 44.

The structure analyses of racemic 3‐chloro‐1‐(4‐morpholino‐5‐nitro­imidazol‐1‐yl)­propan‐2‐ol, C₁₀H₁₅ClN₄O₄, (II), and 3‐chloro‐1‐(5‐morpholino‐4‐nitro­imidazol‐1‐yl)­propan‐2‐ol, C₁₀H₁₅ClN₄O₄, (III), have been undertaken in order to determine the position of the morpholine residue in these two isomers. The morpholine residue in (II) is connected at the 4‐position, while in (III), it is connected at the 5‐position of the imidazole ring. The morpholine mean planes and nitro groups in the two compounds deviate from the imidazole planes to different extents. The nitro groups in (II) and (III) take part in the conjugation system of the imidazole rings. In consequence, the exocyclic C—N bonds are significantly shorter than the normal single Csp²—NO₂ bond and the nitro groups in (II) and (III) show an extraordinary stability on treatment with morpholine and piperidine [Gzella, Wrzeciono & Pöppel (1999). Acta Cryst. C 55 , 1562–1565]. In the crystal lattice, the mol­ecules of both compounds are linked by O—H?N and C—H?O intermolecular hydrogen bonds.     

Fluordiazadiphosphetidine, 16. Mitt.

The reaction of (CH₃NPF₃)₂ with NH₃ and primary aliphatic and aromatic amines in the molar ratio 3:2 yields (CH₄NPF₄)₂ and the monoamino substituted fluordiaza-diphosphetidines. These react with N-Trimethylsilyl-methylamine to the mixed diamino substituted compounds.With 1,4-Diazabicyclo[2.2.2]octan as HF-acceptor a second step of nucleophilic substitution with NH₃ and primary amines is possible. In the case of ammonia a by- product has been identified as the 1:1 adduct of (CH₃NPF₂NH₂)₂ with 1,4-diazabicyclo[2.2.2]octan.

Herrn Prof. Dr.O. Hromatka zum 80. Geburtstag gewidmet.     

Direct synthesis of fluorinated peroxides. 9. Some reactions of perfluorotertiarybutyl hydroperoxide.

The reaction of (CF₃)₃COOH with perfluoroacyl fluorides in the pressure of NaF results in the formation of new peroxy esters of the type, (CF₃)₃COOC(O)R_f. Addition of the hydroperoxide to CF₃NCF₂ yields the unstable amine (CF₃)₃COOCF₂N(H)CF₃. These reactions of (CF₃)₃COOH are compared with analogous reactions of CF₃OOH and SF₅OOH.     

Antimon-organo-Verbindungen. V. Zum Reaktionsverhalten des Phenylstibins

Organoantimony Compounds. V. The Reactivity of Phenyl Stibine C₆H₅SbH₂, synthesized by the reduction of C₆H₅SbCl₂ with LiBH₄, reacts with LiR under certain conditions forming (C₆H₅Sb)_n and H₂ or give by a partially elimination of H₂ stibides with a different structure. The latter react with alkyl and aryl halides forming tert. stibines which may be characterized as the corresponding dibromides. The preparation of C₆H₅SbNa₂ and its reaction with C₂H₅Br, Cl(CH₂)₄Cl and C₆H₅(Cl)C?N? N?C(Cl)C₆H₅ are described.     

Polysulfonylamine. VII. Aliphatische Trisulfonylamine

Polysulfonyl Amines. VII. Aliphatic Trisulfonyl Amines The compounds N(SO₂R¹)₂(SO₂R²) with R¹ = R² = CH₃ ( 2a ), R¹ = R² = C₂H₅ ( 2b ) and R¹ = CH₃, R² = C₂H₅ ( 2c ) are prepared by cleavage of aminostannanes (CH₃)₃SnN(SO₂R¹)₂ with sulfonyl chlorides R²SO₂Cl. A simple synthesis of 2a from AgN(SO₂CH₃)₂ and CH₃SO₂Cl is described. From the vibrational spectra of 2a , evidence is obtained for a planar NS₃ group in this compound. X-ray structure determinations of 2b and HN(SO₂C₂H₅)₂ ( 3 ) are reported. In 2b , the NS₃ group is approximately planar (S? N? S bond angles 119.0 ± 0.6°, sum of bond angles at N 356.9°); the S? N bond lengths of ca. 173 pm indicate a bond order of 1. In compound 3 , the nitrogen atom has a planar coordination (S? N? S angle 125.3°, sum of bond angles at N 359.3°), the S? N bond lengths of ca. 165 pm correlate with a bond order of 1.3? 1.4.     

Bildung siliciumorganischer Verbindungen. LXII. Teilbromierte Carbosilane

Formation of Organosilicon Compounds. LXII. Partial Brominated Carbosilanes The photobromination of 1 leads to compound 2 as well as to C-chlorinated derivatives if the time of reaction is prolonged. Compound 2 is also formed from (Br₂Si–CH₂)₃; Gl. (1) see ?Inhaltsübersicht”?. In a corresponding reaction (Cl₃Si–CH₂)₂SiCl₂ gives successively Cl₃Si–CHBr–SiCl₂–CH₂–SiCl₃, Cl₃Si–CBr₂–SiCl₂–CH₂–SiCl₃ and Cl₃Si–CCl₂–SiCl₂–CH₂–SiCl₃. (Cl₃Si)₂CBr₂ is accessible through the photobromination of (Cl₃Si)₂CH₂. The reactivity of the CBr₂-group is quite obvious in the reaction of Cl₂Si–CBr₂–SiCl₂–CH₂–SiCl₃ with LiAlH₄ yielding (H₃Si–CH₂)₂SiCl₂ as well as in the reaction of compound 2 with CH₃MgCl yielding [(CH₃)₂Si–CH₂]₃. By treatment of the SiH groups with bromine the preparation of compounds with the general formulas CH₃SiH_nBr_3?n; (H_3?nSiBr_n)₂CH₂; (H_3?nSiBr_n? CH₂)₂SiH_2?nBr_n; (H_2?nBr_nSi? CH₂)₃ and (H_3?nSiBr_n)₂CCl₂ is possible. Analysis of the nmr spectra shows that 1,3-Dibromo-1,3,5-trisilacyclohexane is formed to 67% in the trans and to 33% in the cis configuration; 1,3,5-Tribromo-1,3,5-trisilacyclohexane is formed to 80–90% in teh cis-trans configuration. The results of ¹H and ²⁹Si NMR investigations are reported.     

Bildung siliciumorganischer Verbindungen. XXXIX. Teilchlorierte Carbosilane

1. Photochlorination in CCl₄ of the Si-chlorinated carbosilanes (Cl₃Si? CH₂)₂SiCl₂ and (Cl₂Si? CH₂)₃ leads to totally chlorinated compounds, e. g. (Cl₃Si? CCl₂)₂SiCl₂. After chlorination has started at one CH₂ group, formation of a CCl₂ group is preferred before another CH₂ group is involved into the reaction. Thus preparation of compounds a, b, c is possible. Cl₃Si? CCl₂? SiCl₂? CH₂? SiCl₃ (a) for (b) and (c) (see “Inhaltsübersicht”). SO₂Cl₂ (benzoyl peroxide) as chlorinating agent reacts more slowly, and opens an access to carbosilanes containing CHCl groups such as (d), Cl₃Si-CHCl? SiCl₂? CH₂? SiCl₃ (e). Reactions of compounds (a) to (d) with LiAlH₄ yields carbosilanes with SiH groups, and partially chlorinated C atoms. 2. By the high reactivity of Si? CCl₂? Si groups an exchange of Cl atoms of CCl groups in perchlorinated carbosilanes is possible for H atoms of Si? H groups in perhydrogenated carbosilanes, thus allowing the preparation of compounds containing CHCl and SiHCl groups, e. g. according to Gl.(1) (Inhaltsübersicht). Further reactions, formulated as the last equations in Inhaltsübersicht, are reported as well as the rearrangement of H₃Si? CHCl? SiH₃.     

Fluordiazadiphosphetidine, 17. Mitt.

The reactions of (CH₃NPF₃)₂ and F₃P(CH₃N)₂PF₂OCH₃ with lithium-1,1,1-trimethyl-N-(trimethylsilyl)-silanamide yield two new dispiro-compounds:XF₂P(CH₃N)₂PF(NSiCH₃)₂PF(CH₃N)₂PF₂ X withX=F, OCH₃. Synthesis, mass-spectra and X-ray structures are discussed.

Herrn Prof. Dr.K. L. Komarek zum 60. Geburtstag gewidmet.     

Alternativ-Liganden. XXIV. Rhodium(I)-Komplexe mit P-Donor-und Sn- bzw. B-Akzeptor-Liganden

Alternative Ligands. XXIV. Rhodium(I) Complexes with P-Donor and Sn- or B-Acceptor Ligands Donor/acceptor ligands of the type Me₂PCH₂CH₂SnMe₃ (1) , (Me₂PCH₂CH₂)₂SnMe₂ (2) , and Me₂PCMe=CMeBMe₂ (3) , respectively, have been prepared by hydrostannlation of Me₂PVi with Me₃SnH or Me₂SnH₂ and by a multistep synthesis via Na[Me₃BH], Na[Me₃BC?;CMe] using Me₂PCI as partner, respectively. The new ligands were used to produce the Rh(I) complexes RhCI(CO)(Me₂PCH₂CH₂SnMe₃)₂ (5) , RhCI(CO)(Me₂PCH₂CH₂)₂SnMe₂ (7), and RhCI(CO)(Me₂PCMe=CMeBMe₂)₂ (8) by reactions of Rh(CO)₂CH₂ (4) with the corresponding ligands. In addition, the VASKA type compounds RhCI(CO)(Me₂PVi)₂ (6) and RhCI(CO)(PMe₃)₂ were prepared in order to test an alternative route to 5 or to from the known adduct RhCI(CO)(PMe₃)₂. BBr₃ (9) . RhBr(CO)(PMe₃)₂ (10) and the binuclear system [RhBr(CO)PMe₃]₂ (11) were identified spectroscopically after working up the 1:1 reaction mixture of RhCI(CO)(PMe₃)₂ and BBr₃. Reasonable pathways are suggested for their formation. ?Metallbase”?/acceptor interaction show up, on the one hand, in following reactions in case of the ligands with Sn acceptors, on the other hand, in significant changes of spectroscopic data for 8 . New compounds of sufficient stability were characterized by analytical (C, H) and spectroscopic (MS, IR. NMR) investigations.     

Aminophosphane. XI. Einige Reaktionen des N-Diphenylphosphino-triphenyl-phosphazens

N-Diphenylphosphino-triphenylphosphazene possesses a highly reactive (C₆H₅)₂P group. At room temperature CH₃J adds to give (C₆H₅)₃P?N?P(C₆H₅)₂CH ₃J whilst phenylbromide did not react under similar conditions. The phosphorous halides (C₆H₅)₂PX(X = Cl, Br)add in a 1:1 mole ratio to yield (C₆H₅)₃P?N?P(C₆H₅)₂? PC₆H₅)₂X; this addition is also the preferred reaction with C₆H₅PCl₂, but PCl₃ is in part dehalogenated by (C₆H₅)₃P?N? P(C₆H₅)₂, and PSCl₃ desulfurized. The chalcogens O, S, Se, Te readily add to the P(III) atom of the base and this is also the case with BH₃. CS₂ forms the betaine (C₆H₅)₃ · · P?N? P(C₆H₅)₂? C(S)S. The IR and NMR spectra of the new compounds are discussed.     

Neue Verbindungen mit Granatstruktur. VI. Vanadate

New Compounds with Garnet Structure. VI. Vanadates The preparation of vanadate-garnets of the following three types is reported: (I) {Na₃}[B₂^III](V₃)O₁₂ (B^III = Cr, Sc), (II) {LiCa₂}[B₂^II](V₃)O₁₂ (B^II = Mg), (III) {Ca₂A^III}[Li₂] (V₃)O₁₂ (A^III = In, Sc). The Cr-compound of type (I) decomposes above 690°C into a mixture of Cr₂O₃ and NaVO₃. The analogous Fe-compound decomposes in a similar way already at 400°C; therefore the preparation by solid state reaction is not possible. Employing larger B^III-ions (Y, Yb, Lu) no garnets of type (I), but mixtures of B^IIIVO₄ (zircon structure) and Na₃B^IIIV₂O₈ are formed. Garnets of type (II) do not exist, when B^II are Co and Ni. Mixtures of {Ca₃}[LiB^II](V₃)O₁₂ (garnet structure), LiB^IIVO₄ (spinel structure) and B₃^II(VO₄)₂ are formed. With type (III) for A^III = Y reaction occurs forming a mixture of YVO₄, Ca₃(VO₄)₂ and Li₃VO₄.     

Azole. 45.

The three title compounds, namely (Z)‐1‐(4,5‐di­nitro­imidazol‐1‐yl)‐3‐morpholinopropan‐2‐one 2,4‐di­nitro­phenyl­hydrazone, C₁₆H₁₇N₉O₉, (IV), (Z)‐3‐morpholino‐1‐(4‐morpholino‐5‐nitro­imidazol‐1‐yl)propan‐2‐one 2,4‐di­nitro­phenyl­hydrazone, C₂₀H₂₅N₉O₈, (Va), and (E)‐3‐morpholino‐1‐(4‐morpholino‐5‐nitro­imidazol‐1‐yl)propan‐2‐one 2,4‐di­nitro­phenylhydra­zone tetra­hydro­furan solvate, C₂₀H₂₅N₉O₈·C₄H₈O, (Vb), have been prepared and their structures determined. In (IV), the C‐4 nitro group is nearly perpendicular to the imidazole ring and the C‐4—NO₂ bond length is comparable to the value for a normal single Csp²—NO₂ bond. In (IV), (Va) and (Vb), the C‐­5 nitro group deviates insignificantly from the imidazole plane and the C‐5—NO₂ bond length is far shorter in all three compounds than C‐4—NO₂ in (IV). In consequence, the C‐4 nitro group in (IV) is easily replaced by morpholine, while the C‐5 nitro group in (IV), (Va) and (Vb) shows an extraordinary stability on treatment with the amine. The E configuration in (Vb) is stabilized by a three‐centre hydrogen bond.