Synthesis and characterization of spiro-, ansa-, and spiro-ansa-cyclic derivatives of cyclotetraphosphazene with the reactions of pentane-1,5-diol

The reactions of octachlorocyclotetraphosphazatetraene, N₄P₄Cl₈ (1) with difunctional aliphatic reagent, HO-(CH₂)₅-OH (3) have aroused a good deal of attention, and four types of products have been realized: one 2-open chain-(1′-oxy-5′-hidroxy-pentane)-2,4,4,6,6,8,8-heptachlorocylotetraphosphazatetraene, N₄P₄Cl₇[O(CH₂)₅OH] (4); one 2,2-mono-spiro-(1′,5′-pentanedioxy)-4,4,6,6,8,8-hexachlorocyclotetraphosphazatetraene, N₄P₄Cl₆[O(CH₂)₅O] (5); its isomers 2,4-mono-ansa-((1′,5′-pentanedioxy)-2,4,6,6,8,8- hexachlorocyclotetraphosphazatetraene (6) and 2,6-mono-ansa-(1′,5′-pentanedioxy)-2,4,6,6,8,8-hexachlorocyclotetraphosphazatetraene (7); one 2,2,6,6-dispiro-(1′,5′-pentanedioxy)-4,4,8,8-tetrachlorocyclo- tetraphosphazatetraene, N₄P₄Cl₄[O(CH₂)₅O]₂ (8); two isomeric 2,4,6,8-bisansa-(1′,5′-pentanedioxy)-2,4,6,8-tetrachlorocyclotetraphosphazatetraene (9) and 2,6,4,8-bisansa-(1′,5′-pentanedioxy)-2,4,6,8-tetrachloro-cyclotetraphosphazatetraene (10); one 4,4,8,8-dispiro-2,6-ansa- (1′,5′-pentanedioxy)-2,6-dichlorocyclotetra-phosphazatetraene, N₄P₄Cl₂[O(CH₂)₅O]₃ (11), one 2,2,4,4,6,6-trispiro-(1′,5′-pentanedioxy)-8,8-dichlorocyclo-tetraphosphazatetraene, N₄P₄Cl₂[O(CH₂)₅O]₃ (12); and a 2,2,4,4,6,6,8,8-tetraspiro-(1′,5′-pentanedioxy)-cyclotetraphosphazatetraene derivative, N₄P₄[O(CH₂)₅O]₄, (13). The respective structures were deduced by means of elemental analysis, mass spectrum, and ³¹P, ¹H, and ¹³C nuclear magnetic resonance spectroscopic investigations.     

Phosphorus-nitrogen compounds: Reinvestigation of the reactions of hexachlorocyclotriphosphazene with 1,4-butane- and 1,6-hexane-diols—NMR studies of the products

Reactions of hexachlorocyclotriphosphazene N₃P₃Cl₆ (1) with 1,4-butane-(2) and 1,6-hexane-diols (3) in (1:1:2, 1:2:4, and 1:3:6) stoichiometries in THF solution at room temperature (r.t.) and under refluxing conditions yield a total of 15 products: two open chain, N₃P₃Cl₅[O(CH₂)_nOH] (n = 4, 6) (4, 5), two mono-spiro, N₃P₃Cl₄[O(CH₂)_nO] (n = 4, 6) (6, 7), two mono-ansa, N₃P₃Cl₄[O(CH₂)_nO] (n = 4,6) (8, 9), two dispiro, N₃P₃Cl₂[O(CH₂)_nO]₂ (n = 4, 6) (10, 11), two spiro-ansa, N₃P₃Cl₂[O(CH₂)_nO]₂ (n = 4, 6) (12, 13), one tri-spiro, N₃P₃[O(CH₂)₄O]₃ (14), two single-bridged, N₃P₃Cl₅[O(CH₂)_nO]N₃P₃Cl₅ (n = 4, 6) (15, 16), one double-bridged, N₃P₃Cl₄[O(CH₂)₆O]₂N₃P₃Cl₄ (17), and one tri-bridged, N₃P₃Cl₃[O(CH₂)₆O]₃N₃P₃Cl₃ (18) derivatives. Their structures have been elucidated by MS, ³¹P, and ¹H NMR spectroscopy. The results obtained, based on the synthesis, characterization, product types, and the relative yields, are compared with those of previous studies on the reactions of 1 with 1,2-ethane-, 1,3-propane-, 1,4-butane-, 1,5-pentane-, and 1,6-hexane-diols.     

The reactions of non-gem-hexanedioxytetrachlorocyclotriphosphazene with 2-(2-hydroxyethyl)thiophene,benzyl alcohol and 1,1,3,3-tetramethylguanidine. Spectroscopic studies of the derived products

Abstract

Reactions of non-gem-hexanedioxytetrachlorocyclotriphosphazene (1) with monofunctional nucleophilic reagents, 2-(2-hydroxyethyl)thiophene (2), benzyl alcohol (3) and 1,1,3,3-tetramethylguanidine (4) were investigated. The reactions, using an excess of NaH, in THF solutions, under refluxing conditions and with 1:2?mole ratios allow the synthesis of the following novel cyclotriphosphazene derivatives: 2,4-dichloro-2,4-(hexane-1,6-dioxy)-6,6-[2-(2-ethoxy)hiophene]-cyclotriphosphazatriene, N₃P₃Cl₂[O(CH₂)₆O-(C₆H₈OS)₂] (5); 2,4-(hexane-1,6-dioxy)-2,4,6,6-[2-(2-ethoxy) thiophene]-cyclotriphosphazatriene, N₃P₃[O(CH₂)₆O-(C₆H₈OS)₄] (6); 2,4-dichloro-2,4-(hexane-1,6-dioxy)-6,6-(methoxybenzene)-cyclotriphosphazatriene, N₃P₃Cl₂[O(CH₂)₆O-(C₆H₅CH₂O)₂] (7); 2,4-(hexane-1,6-dioxy)-2,4,6,6-(methoxybenzene)-cyclotriphosphazatriene, N₃P₃[O(CH₂)₆O-(C₆H₅CH₂O)₄] (8); and 2,4-dichloro-2,4-(hexane-1,6-dioxy)-6,6-(1,1,3,3-tetramethyguanidine)-cyclotriphosphazatriene, N₃P₃Cl₂[O(CH₂)₆O-HN-CN₂(CH₃)₄] (9). The structures of the synthesized compounds (5–9) have been characterized by elemental analysis, TLC-MS, ¹H, ¹³C and ³¹P {+¹H} and {?¹H} NMR spectral data.     

Reactions of cyclochlorotriphosphazatriene with 2-mercaptoethanol. Calorimetric and spectroscopic investigations of the derived products

Abstract

The reactions of hexachlorocyclotriphosphazatriene, N₃P₃Cl₆ (1) with 2-mercaptoethanol, 2-HS-CH₂-CH₂-OH (2), in (1:1, 1:2 and 1:3) mole ratios, in excess of NaH, in THF and diethylether solutions yield a total of 6 novel products: one mono spiro, N₃P₃Cl₄[O-CH₂-CH₂-S] (3); one mono-substituted open chain, N₃P₃Cl₅[S-CH₂-CH₂-OH] (4); one dispiro, N₃P₃Cl₂[O-CH₂-CH₂-S]₂ (5); one tri-substituted open chain, N₃P₃Cl₃[S-CH₂-CH₂-OH]₃ (6); one tris-spiro, N₃P₃[O-CH₂-CH₂-S]₃ (7) and one disubstituted open chain, N₃P₃Cl₄[S-CH₂-CH₂-OH]₂ (8) derivatives. The spiro products (3, 5 and 7) are formed as the major products in this system and all of the synthesized compounds are found to be stable at room temperature. The structures of the derived compounds were elucidated by elemental analysis, TLC-MS, ³¹P and ¹H NMR spectral data. For evaluation of melting behavior of derivatives (6) and (7), thermal transition peaks and their corresponding enthalpies were determined via DSC technique.     

Phosphorus-Nitrogen Compounds: The Reactions of Hexachlorocyclotriphosphazatriene with Pentane-1,5-Diol. Nuclear Magnetic Resonance Studies of The Products

Abstract

From the reactions of hexachlorocyclotriphosphazatriene, N₃P₃Cl₆ (1) with pentane-1,5-diol (2) in dichloromethane solution, the following derivatives have been isolated: 2,2-spiro(1′,5′-pentanedioxy)-4,4,6,6-tetrachlorocyclotriphosphazatriene, N₃P₃Cl₄[O(CH₂)₅O] (3); its ansa isomer, 1,3-ansa(1′,5′-pentanedioxy)-1,3,5,5-tetrachlorocyclotriphosphazatriene, (4); bis spiro(1′,5′-pentanedioxy)-6,6-dichlorocyclotriphosphazatriene, N₃P₃Cl₂[O(CH₂)₅O]₂ (5); its spiro-ansa isomer, (1′,5′-pentanedioxy)-1,3-dichlorocyclotriphosphazatriene (6); as well as the bino(1,5-pentanedioxy)-di-(pentachlorocyclotriphosphazatriene), N₃P₃Cl₅ [O(CH₂)₅O]N₃P₃Cl₅ (7), and tri-bino(1,5-pentanedioxy)-di (trichlorocyclotriphosphazatriene), N₃P₃Cl₃[O(CH₂)₅O]₃N₃P₃Cl₃, (8) derivatives. Their structures were established by MS and NMR with the use of ¹H, ¹³C, and ³¹P spectroscopy. Product types and relative yields are compared with those of the previously investigated diol derivatives. The yield of the mono-ansa product (25%) obtained in this system was considerably increased relative to those of the propane-1,3-diol derivative (11.2%) and decreased relative to the 2,2-dimethyl-propane-1,3-diol (36.2%), and bis(2-hydroxyethyl) ether (34.5%) derivatives.     

Synthesis and Structural Characterization of Singly,Doubly, and Triply Bridged Derivatives of Hexachlorocyclotriphosphazene with Bis(2-hydroxyethyl) Ether and 2,2-dimethylpropane-1,3-diol

Abstract

The reactions of hexachlorocyclotriphosphazene, N₃P₃Cl₆ (1), with 2,2-dimethylpropane-1,3-diol (2), and bis(2-hydroxyethyl) ether (3) have been previously reported. Although both reactions gave the expected spiro, ansa, and bridged type products, open-chain and triply bridged derivatives from both systems and singly bridged derivatives from 2,2-dimethylpropane-1,3-diol (2) were not isolated, and doubly bridged compounds were only detected in trace amounts in both systems. However, in a subsequent reinvestigation in tetrahydrofuran (THF) solution, the reaction of 1 with the diols 2 and 3 gave the open chain compounds N₃P₃Cl₅[O(CH₂)₂CMe₂OH] (4) and N₃P₃Cl₅[(OCH₂CH₂)₂OH] (5), the singly bridged compound N₃P₃Cl₅[(OCH₂)₂-CMe₂]N₃P₃Cl₅ (6), the doubly bridged compounds N₃P₃Cl₄[(OCH₂)₂CMe₂]₂N₃P₃Cl₄ (8) and N₃P₃Cl₄[(OCH₂CH₂)₂O]₂N₃P₃Cl₄ (9), and the triply bridged compounds N₃P₃Cl₃[(OCH₂)₂-CMe₂]₃N₃P₃Cl₃ (10) and N₃P₃Cl₃[(OCH₂CH₂)₂O]₃N₃P₃Cl₃ (11).

The doubly bridged derivatives were also isolated in better yields relative to earlier reports. The substituted cyclotriphosphazenes have been characterized by elemental analysis, mass spectrometry, as well as by ¹H, ³¹P, and ¹³C NMR spectroscopy. It is found that with variation of the solvent there is a decrease in the product formed by intramolecular reactions (spiro and ansa derivatives) and a concomitant increase in the amount of products formed by intermolecular reactions (singly, doubly, and triply bridged derivatives) of cyclophosphazene.     

Synthesis and structural characterization of geminal and non-geminal 1,1,3,3-tetramethylguanidine substituted derivatives of cyclotriphosphazene: Thermal and spectroscopic investigations of the products

Abstract

The reactions of hexachlorocyclotriphosphazene, N₃P₃Cl₆ (1) with 1,1,3,3-tetramethyl-guanidine (2) in (1:1:2, 1:2:4 and 1:3:6) stoichiometries in THF and dichloromethane solutions under reflux yield a total of 4 novel products: three non-geminal derivatives, N₃P₃Cl₄[NCN₂(CH₃)₄]₂ (3), N₃P₃Cl₃[NCN₂(CH₃)₄]₃ (4) and N₃P₃Cl₂[NCN₂(CH₃)₄]₄ (5); and one hexa-substituted product, N₃P₃[NCN₂(CH₃)₄]₆ (6). The structures of 3-6 have been determined mainly by elemental analysis, MS, ³¹P and ¹H NMR spectral data. Furthermore, thermal characteristics of the synthesized compounds 4 and 6 were evaluated using Differential Scanning Calorimetric (DSC) measurements. NMR spectroscopic data, product types and relative yields are compared with those of the previously investigated derivatives of N₃P₃Cl₆ (1) with mono and difunctional reagents.     

THE B.A.S.I.C. (BINO-ANSA-SPIRO-IN-CYCLOPHOSPHAZENES) SYSTEM. PART I: NEW DERIVATIVES OF THE BIS-(TETRACHLORO-CYCLOTRIPHOSPHAZENYL)-SPERMINE

Abstract

The synthesis of new derivatives of bis-(tetrachlorocyclotriphosphazenyl)-spermine was achieved upon reaction of some MONOSPIRO–N₃P₃Cl₄[HN–(CH₂) _n –NH] (n = 2,3,4) derivatives and of the gem–N₃P₃Az₂Cl₄ with spermine. All compounds were obtained in the monomeric state. ³¹P and ¹³C high-resolution NMR were used, together with IR spectroscopy and mass spectrometry, to assign molecular structures and to reveal conformational equilibria, if any.     

Synthesis,crystal structure and catalytic performance of bis (imino)pyridyl nickel complexes

Two new Ni(II) complexes of 2,6-bis[1-(2,6-diethylphenylimino)ethyl]pyridine (L¹), 2,6-bis[1-(4-methylphenylimino)ethyl]pyridine (L² ) have been synthesized and structurally characterized. Complex Ni(L¹)Cl₂?·?CH₃CN (1), exhibits a distorted trigonal bipyramidal geometry, whereas complex Ni(L¹)(CH₃CN)Cl₂ (2), is six-coordinate with a geometry that can best be described as distorted octahedral. The catalytic activities of complexes 1, 2, Ni{2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine} Cl₂?·?CH₃CN (3), and Ni{2,6-bis[1-(2,6-dimethylphenylimino) ethyl]pyridine}Cl₂?·?CH₃CN (4), for ethylene polymerization were studied under activation with MAO.     

Bildung und NMR-spektroskopische Charakterisierung von Alk-(ar-)oxyderivaten von Trichlorphosphazen-N-phosphoryldichlorid,Cl3PN?P(O)Cl2, Imido- und N-Methylimidodiphosphoryltetrachlord,Cl2P(O)NHP(O)Cl2 bzw. Cl2P(O)N(CH3)P(O)Cl2

Formation and N.M.R.-Spectroscopic Characterization of Alk-(ar-)oxy Derivatives of Trichlorophosphazene-N-phosphoryldichloride, Cl₃P?N? P(O)Cl₂, Imido- and N-Methylimidodiphosphoryltetrachloride, Cl₂P(O)NHP(O)Cl₂ and Cl₂P(O)N(CH₃)P(O)Cl₂ The ester chlorides and esters P₂NOCl_5?x(OR)_x (x = 1?5), P₂(NH)O₂Cl_4?x(OR)_x (x = 1–4) and P₂(NCH₃)O₂Cl_4–x(OR)_x (x = 1–4) derived from the title compounds by substitution of chlorine atoms by alk- or aroxy groups are characterized by their ³¹P-n.m.r. data. The possibilities for forming these compounds by alcoholysis, chloridolysis, dealkylation and P? N-bond formation are discussed.     

New polyfunctional silicon-containing amines C6[CH2CH2SiMe(OCH2CH2NR2)2]6 (R = H,Me) and their reactions with cobalt(ii) chloride and dicobalt octacarbonyl

Hexakis[bis(2-aminoethoxy)methylsilylethyl]benzene and hexakis[bis(N,N-dimethyl-2-aminoethoxy)methylsilylethyl]benzene C₆[(NR₂CH₂CH₂O)₂SiMeCH₂CH₂]₆ (4, R = H; 5, R = Me) were prepared from hexakis(methyldichlorosilylethyl)benzene C₆(Cl₂MeSiCH₂CH₂)₆ and 2-aminoethanol or N,N-dimethyl-2-aminoethanol, respectively. Compounds 4 and 5 react with anhydrous cobalt (ii) chloride to give poorly soluble dodecachloro{hexakis[bis(2-aminoethoxy)methylsilylethyl]benzene}hexacobalt and dodecachloro{hexakis[bis(N,N-dimethyl-2-aminoethoxy)methylsilylethyl]benzene}hexacobalt {Co₆[(NR₂CH₂CH₂O)₂SiMeCH₂CH₂]₆C₆}Cl₁₂ (R = H or Me), respectively. Polyfunctional amine 4 reacts with dicobalt octacarbonyl to produce hexakis[bis(2-aminoethoxy)methylsilylethyl]benzenedicobalt(ii) tetrakis(tetracarbonylcobaltate) {Co₂[(NH₂CH₂CH₂O)₂SiMeCH₂CH₂]₆C₆}[Co(CO)₄]₄. N,N-Dimethyl-substituted polyfunctional amine 5 is lowly reactive in the reaction with Co₂(CO)₈, whereas the simplest model of this compound, viz., bis(N,N-dimethyl-2-aminoethoxy)dimethylsilane (NMe₂CH₂CH₂O)₂SiMe₂, slowly reacts with Co₂(CO)₈ to give tris[bis(N,N-dimethyl-2-aminoethoxy)dimethylsilane]cobalt(ii) bis(tetracarbonylcobaltate) {Co[(NMe₂CH₂CH₂O)₂SiMe₂]₃}[Co(CO)₄]₂. Thermal decomposition and transformations of the resulting complexes under the action of oxygen and water were studied.     

Single-, double- and triple-bridged derivatives of cyclotriphosphazenes with an octafluorohexane-1,6-diol

Reaction of hexachlorocyclotriphosphazene, N₃P₃Cl₆ (1), with the sodium derivative of the fluorinated diol, 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol, (2), in THF solution at room temperature afforded five products, whose structures have been characterised by ¹H, ¹⁹F and ³¹P NMR spectroscopy: the mono-ansa compound N₃P₃Cl₄[OCH₂(CF₂)₄CH₂O] (3); the single-bridged compound N₃P₃Cl₅[OCH₂(CF₂)₄CH₂O]N₃P₃Cl₅ (4), two double-bridged compounds N₃P₃Cl₄(OCH₂(CF₂)₄CH₂O)₂N₃P₃Cl₄, (5-anti, 5-syn) and the triple-bridged compound N₃P₃Cl₃(OCH₂(CF₂)₄CH₂O)₃N₃P₃Cl₃ (6). X-ray crystallographic studies confirmed the structures of the ansa compound (3), the double-bridged compound (5-anti) and the first example of a triple-bridged cyclotriphosphazene derivative (6). The results were also compared with those for reactions of (1) with analogous fluorinated shorter diols (1,4-butane- and 1,5-pentane-diols). It is found that on increasing the chain length of the diol, there is a decrease in the relative proportion of intramolecular reactions giving spiro and ansa derivatives and an increase in the amount of bridged cyclophosphazene derivatives via intermolecular reactions.     

Preparation,Spectroscopic and Structural Investigations of Spiro Derivatives of Hexachlorocyclotriphosphazatriene

Abstract

Mono-(N₃P₃Cl₄Y₂), bis-(N₃P₃Cl₂Y₄) and tris-spiro derivatives (N₃P₃Y₆) have been prepared with ethylene, 1, 3-propylene and 1,4-butylene glycols (Y₂ = glycol residue). The ¹H NMR spectra of mono- and tris-derivatives are relatively simple; those of the bis- very complex due to the intrinsic asymmetry of the methylene protons. This effect is made use of in studying the replacement pattern of N₃P₃Cl₄ [O (CH₂)₃O] with primary and secondary amines. Homonuclear ¹H decoupling simplifies the spectra and allows an unambiguous distinction to be made between the different isomeric possibilities of the bis amino derivatives N₃P₃Cl₂R₂ [O(CH₂)₃O] where R = amino residue. Primary amines give geminal, secondary amines nongeminal trans-derivatives. The trans-structure of the bis-pyrrolidino derivative has been confirmed by X-ray crystallography.     

Effect of chain length on the formation of intramolecular and intermolecular products: Reaction of diols with cyclotriphosphazene

The reactions of cyclotriphosphazene, N₃P₃Cl₆ (1), in a 1:1.2 stoichiometry with the sodium derivative of seven diols [ethane- (2a), 1,3-propane- (2b), 1,4-butane- (2c), 1,5-pentane- (2d), 1,6-hexane- (2e), 1,8-octane- (2f) and 1,10-decane- (2g) diol] in THF solution at room temperature have been used to investigate the effect of chain length on the formation of reaction products. Although no new products were found for the reaction of 1 with diols 2a-c compared to those in the literature using other bases and solution conditions, the reactions of 1 with the diols 2d-g gave six different types of products, whose structures have been characterized by elemental analysis, mass spectrometry, ¹H and ³¹P NMR spectroscopy; ansa compounds N₃P₃Cl₄[O(CH₂)_nO], (5d-5g); single-bridged compounds N₃P₃Cl₅[O(CH₂)_nO]N₃P₃Cl₅(6d-6f); double-bridged compounds N₃P₃Cl₄[O(CH₂)_nO]₂N₃P₃Cl₄ (7d-7g, syn and anti) and triple-bridged compounds, N₃P₃Cl₃[O(CH₂)_nO]₃N₃P₃Cl₃ (8d-f). Where suitable single crystals were obtained, X-ray crystallographic studies confirmed the structures of two ansa compounds (5d and 5f), one single-bridged compound (6e), and five double-bridged compounds (meso-anti for 7d, 7e, 7f and meso-syn for 7d and 7f). ³¹P NMR measurements of the reaction mixtures were used to quantify the formation of products for the reactions 1 with all the diols, 2a-g; it is found that, with increasing chain length of the diol, there is a decrease in the products formed by intramolecular reactions (spiro and ansa derivatives) and a concomitant increase in the amounts of products formed by intermolecular reactions (single-, double- and triple-bridged derivatives) of cyclophosphazene.     

Supramolecular inclusion of a pillared double-layered host by an anion-directed second-sphere coordination

In this paper, we have illustrated the utilisation of a second-sphere coordination approach to construct supramolecular inclusion solids with varieties of guest molecules. A flexible molecule N,N,N′,N′-tetra-p-methylbenzyl-ethylenediamine (L1) bearing doubly protonated H-bond donors was designed, capable of forming N–H…Cl hydrogen bonds with a crystallographically unique chloride anion, to construct an anion-directed ligand. The pillared double-layered host framework was constructed by an anion-directed ligand and primary coordination sphere [CoCl₄]^2 ?  through weak C–H…Cl hydrogen-bonding interactions. A variety of guest molecules, such as p-anisaldehyde, 1,4-dimethoxy-2,5-bis(methoxymethyl)benzene, can be included, leading to the formation of novel supramolecular inclusion solids: [L1]·4[H]⁺·[CoCl₄]^2 ? ·2Cl^? ·1.5[C₈H₈O₂]·0.25[CH₃OH] (1) and [L1]·4[H]⁺·[CoCl₄]^2 ? ·2Cl^? ·1.5[C₁₂H₂₀O₄]·0.5[CH₃OH] (2).

We have presented herein the utilisation of a second-sphere coordination approach to construct supramolecular inclusion solids with a variety of guest molecules. A novel type of a pillared double-layered host framework was constructed by a second-sphere coordination between the anion-directed ligand (L1 = N,N,N′,N′-tetra-p-methylbenzyl-ethylenediamine) and [CoCl₄]^2 ?  through weak C–H…Cl hydrogen-bonding interaction, and a variety of guest molecules, such as p-anisaldehyde, 1,4-dimethoxy-2,5-bis(methoxymethyl)benzene, can be included, leading to the formation of supramolecular inclusion solids: [L1]·4[H]⁺·[CoCl₄]^2 ? ·2Cl^? ·1.5[C₈H₈O₂]·0.25[CH₃OH] (1) and [L1]·4[H]⁺·[CoCl₄]^2 ? ·2Cl^? ·1.5[C₁₂H₂₀O₄]·0.5[CH₃OH] (2)

     

Die Chlorooxoarsenate(III) (PPh4)2[As4O2Cl10] · 2 CH3CN und (PPh4)2[As2OCl6] · 3 CH3CN

The Chlorooxoarsenates(III) (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN and (PPh₄)₂[As₂OCl₆] · 3 CH₃CN (PPh₄)₂[As₂Cl₈] can be prepared from As₂O₃, SOCl₂ and PPh₄Cl in acetonitrile. Its oxidation with chlorine yields PPh₄[AsCl₆]. This was also obtained directly from arsenic, chlorine and PPh₄Cl, (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN being a side product; the latter was obtained with high yield from AsCl₃, As₂O₃ and PPh₄Cl in acetonitrile. By addition of PPh₄Cl it was converted to (PPh₄)₂[As₂OCl₆] · 3 CH₃CN. According to their X-ray crystal structure analyses, both crystallize in the triclinic space group P 1. The [As₄O₂Cl₁₀]^2– ion can be regarded as a centrosymmetric association product of two Cl₂AsOAsCl₂ molecules and two Cl^– ions, each Cl^– ion being coordinated with all four As atoms. In the [As₂OCl₆]^2– ion the As atoms are linked via the O atom and two Cl atoms.     

Molybdänhalogenidcluster mit sechs terminalen Alkoholatliganden: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH und (C18H36N2O6Na2)2[Mo6Cl8(OC6H5)6]

Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6CH₃OH and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] . The reaction of Na₂[Mo₆Cl₈(OCH₃)₆] and 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6 CH₃OH ( 1 ), which is converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo₆Cl₈ⁱ(OR^a)₆]^2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo₆Cl₈(OC₆H₅)₆]^2? is investigated by means of UV/VIS spectroscopy and EHMO calculations.     

Preparation of Tellurium‐Nitrogen containing Moieties in Ionic Chainmolecules,Heterocycles, as well as (CF3Se)2Te, (CF3S)2Se,and (CH3)2Te(X)Y (X = Y = NCO,NSO; X = Cl,Y = NSO)

The reaction between Cl₂Te(NSO)₂, Cl₆Te₂N₂S and Cl₂Te(N=S=N)₂TeCl₂ with MCl₃ provided the compounds [(Cl₂Te)₂N⁺][MCl₄^–] (M = Ga, Al, Fe). Treating Cl₆Te₂N₂S with M′Cl₃ yielded besides [(Cl₂Te)₂N⁺][M′Cl₄^–] (M′ = Al, Fe) the sulfur containing compound [ClTeNSNS⁺][M′Cl₄^–]. The structure for [ClTeNSNS⁺][FeCl₄^–] was established by an X‐ray structure analysis. With Te(NSO)₂ and CF₃SCl, via Cl₂Te(NSO)₂, the known compound Te₂NCl₅ was formed. Tetrafluoroditelluradiazetidine was obtained from TeF₄ and [(CH₃)₃Si]₂NH which on treating with (CH₃)₃SiCl provided the corresponding chloroderivative. In addition metathetical reaction between Cl₂TeNSNS and CF₃C(O)OAg yielded [CF₃C(O)O]₂TeSNSN. Similarly (CH₃)₂Te(NSO)_2–xCl_x (x = 0,1) and (CH₃)₂Te(NCO)₂ were made from (CH₃)₂TeCl₂ and AgNSO or AgNCO, respectively. Halogination of Cl₂Te(N=S=N)₂TeCl₂ with Cl₂ or Br₂ yielded Cl₆Te₂N₂S and Cl₄Br₂Te₂N₂S. The bromoderivate was also prepared from Cl₂Te(NSO)₂ and Br₂. AgNSO was synthesized by treating CF₃C(O)OAg with (CH₃)₃SiNSO. Two other synthons (CF₃Se)₂Te and (CF₃S)₂Se were obtained from CF₃SeCl and Na₂Te and from Hg(SCF₃)₂ plus SeCl₄, respectively.     

Darstellung von Tetramethylammoniumazidsulfit und Tetramethylammoniumcyanat‐Schwefeldioxid‐Addukt, [(CH3)4N]+[SO2N3]–, [(CH3)4N]+ [SO2OCN]– und Kristallstruktur von [(CH3)4N]+[SO2N3]–

Preparation of Tetramethylammonium Azidosulfite and Tetramethylammonium Cyanate Sulfur Dioxide‐Adduct, [(CH₃)₄N]⁺[SO₂N₃]^–, [(CH₃)₄N]⁺[SO₂OCN]^– and Crystal Structure of [(CH₃)₄N]⁺[SO₂N₃]^– Tetramethylammonium azide forms with sulfur dioxide an azidosulfite salt. It is characterized by NMR and vibrational spectroscopy and the crystal structure analysis. [(CH₃)₄N]⁺[SO₂N₃]^– crystallizes in the monoclinic space group P2₁/c with a = 551.3(1) pm, b = 1095.2(1) pm, c = 1465.0(1) pm, β = 100.63(1)°, and four formula units in the unit cell. The crystal structure possesses a strong S–N interaction between the N^3– anions and the SO₂ molecules. The S–N distance of 200.5(2) pm is longer than a covalent single S–N bond. The structure is compared with ab initio calculated data. Furthermore an adduct of tetrametylammonium cyanate and sulfur dioxide is reported. It is characterised by NMR and vibrational spectroscopy. The structure is calculated by ab initio methods.