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.     

Synthesis,structural characterization and antimicrobial activities of cyclochlorotriphosphazene derivatives derived from N-(1-Naphthyl)ethylenediamine

Abstract

The nucleophilic substitution reactions of cylochlorotriphosphazene (N₃P₃Cl₆) with N-(1-Naphthyl)ethylenediamine resulted in the following formation of partially and fully substituted cyclotriphosphazene derivatives: 2,4,4,6,6-pentachloro-2-open-chain-N-(1-Naphthyl) ethylendiamino-cyclotriphosphazatriene (3); 4,4,6,6-tetrachloro-2,2-spiro-N-(1-Naphthyl) ethylendiamino-cyclotriphosphazatriene (4); 2,6,6-trichloro-2-open-chain-4,4-spiro-N-(1-Naphthyl)ethylendiamino-cyclotriphosphazatriene (5); 2,4-dichloro-2,4-ansa-6,6-spiro-N-(1-Naphthyl)ethylendiamino)-cyclotriphosphazatriene (6); and 2,4,6-trichloro-2,4,6-non-gem-open-chain-N-(1-Naphthyl)ethylendiamino)-cyclotriphosphazatriene (7); 2,2,4,4,6,6-tri-spiro-N-(1-Naphthyl)ethylendiamino)-cyclotriphosphazatriene (8); 2,4-dichloro-2,4-cis-open-chain-6,6-spiro-N-(1-Naphthyl)ethylendiamino)-cyclotriphosphazatriene (9); and 2,4,6,6-tetrachloro -2,4-ansa-N-(1-Naphthyl)ethylendiamino)-cyclotriphosphazatriene (10). The reactions produced the 4,4,6,6-tetrachloro-2,2-spiro-N-(1-Naphthyl) ethylendiamino-cyclotriphosphazatriene (4) and 2,4,6,6-tetrachloro-2,4-ansa-N-(1-Naphthyl)ethylendiamino)-cyclotriphosphazatriene (10) derivatives as the major products in this system. The structures of the compounds were characterized by FT-IR, elemental analysis, TLC-MS, FT-IR, ¹H, and ³¹P NMR spectral data. All the derived compounds (3–10) were screened for antimicrobial activity by using the broth-agar microdilution technique for the determination of MIC and MCC values. In this context, the compounds were examined against three different human pathogens; Escherichia coli W3110, Staphylococcus aureus ATCC 25923 and Candida albicans ATCC 10231. Except compounds 6 and 9, the rest of the compounds exhibited significant antimicrobial activity on E. coli (W3110), S. aureus (ATCC 25923) and C. albicans (ATCC 1023). Among the synthesized derivatives, compound 4 is the most active agent against the referenced bacteria.     

The reactions of cyclotriphosphazene with 2-(2-hydroxyethylamino)ethanol. Spectroscopic studies of the derived products

Abstract

The reactions of cyclotriphosphazene (1) with 2-(2-hydroxyethylamino)-ethanol (2) were investigated. 2-(2-hydroxyethylamino)-ethanol (2) is a tri-functional reagent consisting of both aliphatic hydroxyl and the secondary amino groups and its nucleophilic substitution reactions with cylotriphosphazene can lead to different product types; open chain, spiro, ansa, bridged and their mixtures. The reactions with one, two and three equimolar ratios of 2-(2-hydroxyethylamino)-ethanol, in the presence of NaH at 0–10?°C and at room temperature gave the following cyclotriphosphazene derivatives: one mono-spiro, N₃P₃Cl₄[O–(CH₂)₂–NH–(CH₂)₂–O] (3, 1:1, r.t.); its isomer mono-ansa (5, 1:1, r.t.); one dispiro, N₃P₃Cl₂[O–(CH₂)₂–NH–(CH₂)₂–O]₂ (4, 1:1, r.t.); its isomer spiro-ansa (6, 1:2, r.t.); and one single-bridged compound with spiro substituted units, N₃P₃Cl₃[O–(CH₂)₂–NH–(CH₂)₂–O]₃N₃P₃Cl₃ (7, 1:3, at 0–10?°C); as well as single-, N₃P₃Cl₅[O–(CH₂)₂–NH–(CH₂)₂–O]N₃P₃Cl₅ (8, 1:2, r.t.), double-, N₃P₃Cl₄[O–(CH₂)₂–NH–(CH₂)₂–O]₂N₃P₃Cl₄ (9, 1:2, r.t.), and tri-bridged, N₃P₃Cl₃[O–(CH₂)₂–NH–(CH₂)₂–O]₃N₃P₃Cl₃ (10, 1:3, at 0–10?°C) derivatives. Triple-bridged derivative is the major product in this system. The structures of the novel-derived compounds were characterized by TLC-MS, FT-IR, elemental analysis, ¹H, and ³¹P NMR spectral.     

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.     

Synthesis,spectral, thermal and crystallographic investigations on oxovanadium(IV) and manganese(III) complexes derived from heterocyclic β-diketone and 2-amino ethanol

Novel mononuclear oxovanadium(IV) and manganese(III) complexes [VO(L¹)₂·H₂O] (1); [VO(L²)₂·H₂O] (2); [VO(L³)₂·H₂O] (3); [Mn(L¹)₂]ClO₄·H₂O (4); [Mn(L²)₂] ClO₄·H₂O (5); [Mn(L³)₂]ClO₄·H₂O (6) were prepared by condensation of 1 mol of VOSO₄·5H₂O or Mn(OAc)₃· 2H₂O with 2 mol of ligand HL¹, HL² or HL³ (where HL¹ = 4-[(2-hydroxy-ethylamino)-methylene]-5-methyl-2- phenyl-2,4-dihydro-pyrazol-3-one; HL²=4-[(2-hydroxy-ethylamino)-methylene]-5-methyl-2-p-tolyl-2,4-dihydro-pyrazol-3-one; HL³=4-{4-[(2-hydroxy-ethyl-amino)-methyl]-3-methyl-5-oxo-4,5-dihydropyrazol-1-yl} benzene sulfonic acid). The resulting complexes were characterized by elemental analyses, molar conductance, magnetic and decomposition temperature measurements, electron spin resonance, FAB mass, IR and electronic spectral studies. From TGA, DTA and DSC, the thermal behaviour and degradation kinetic were studied. Electronic spectra and magnetic susceptibility measurements indicate distorted octahedral stereochemistry of oxovanadium(IV) complexes and regular octahedral stereochemistry of manganese(III) complexes. Hamiltonian and bonding parameters found from ESR spectra indicate the metal ligand bonding is partial covalent. The X-ray single crystal determination of one of the representative ligand was carried out which suggests existence of amine-one tautomeric form in the solid state. The ¹H-NMR spectra support the existence of imine-ol form in solution state. The LC-MS studies sustain the¹H-NMR result. The electronic structure of the same representative ligand was optimized using 6-311G basis set at HF level ab initio studies to predict the coordinating atoms of the ligand.     

Structural studies of diiron complexes with monophosphine ligands tris(4-chlorophenyl)phosphine or diphenyl-2-pyridylphosphine

Four diiron dithiolate complexes with monophosphine ligands have been prepared and structurally characterized. Reactions of (μ-SCH₂CH₂S-μ)Fe₂(CO)₆ or [μ-SCH(CH₃)CH(CH₃)S-μ]Fe₂(CO)₆ with tris(4-chlorophenyl)phosphine or diphenyl-2-pyridylphosphine in the presence of Me₃NO·2H₂O afforded diiron pentacarbonyl complexes with monophosphine ligands (μ-SCH₂CH₂S-μ)Fe₂(CO)₅[P(4-C₆H₄Cl)₃] (1), (μ-SCH₂CH₂S-μ)Fe₂(CO)₅[Ph₂P(2-C₅H₄N)] (2), [μ-SCH(CH₃)CH(CH₃)S-μ]Fe₂(CO)₅[P(4-C₆H₄Cl)₃] (3), and [μ-SCH(CH₃)CH(CH₃)S-μ]Fe₂(CO)₅[Ph₂P(2-C₅H₄N)] (4) in good yields. Complexes 1–4 were characterized by elemental analysis, ¹H NMR, ³¹P{¹H} NMR and ¹³C{¹H} NMR spectroscopy. Furthermore, the molecular structures of 1–4 were confirmed by X-ray crystallography.     

Hexachlorocuprate(II) Anion: Vibration Spectra and Structure

For the complexes (CH₈N₄)₂[CuCl₆], (C₂H₉N₅)₂[CuCl₆] · 2H₂O, and (CH₈N₄O)₄[CuCl₆]Cl₄, where (CH₈N₄)²⁺, (C₂H₉N₅)²⁺, and (CH₈N₄O)²⁺ are the aminoguanidinium, biguanidium, and carbohydrazidium cations, respectively, IR and Raman spectra were taken and analyzed in the region of Cu—Cl vibrations. Polarization measurements of the Raman spectra of (CH₈N₄O)₄[CuCl₆]Cl₄ single crystals were performed with the purpose of assigning the vibrations to symmetry types. Vibration spectra were calculated for the hexachlorocuprate ion in the given series of compounds, and the spectra of the examined complexes were compared with spectra of the previously known compounds incorporating the hexachlorocuprate(II) ion.     

Synthesis of Titanatranes Containing Bis(aryloxo)-(alkoxo)amines and their Use in Catalysis for Ethylene Polymerization

Syntheses of titanatranes containing [(O-2,4-Me₂C₆H₂-6-CH₂)₂-{O(CH₂)_nCH₂}]N³⁻ (n = 1,2) have been explored. Catalytic activity for ethylene polymerization by Ti₂(OⁱPr)₂{[(O-2,4-Me₂C₆H₂-6-CH₂)₂(µ₂-OCH₂-CH₂)]N}₂ ( 1a ) - MAO catalyst increased at high temperature; the activity also increased upon addition of AlMe₃. Ti(O- 2,6-ⁱPr₂C₆H₃){[(O-2,4-Me₂C₆H₂-6-CH₂)₂(OCH₂CH₂)]N} ( 1c ) showed higher activity than 1a under the same conditions. Ti{[(O-2,4-Me₂C₆H₂-6-CH₂)₂(HOCH₂CH₂CH₂)]N}₂ was isolated from the reaction of Ti(OⁱPr)₄ with bis(2-hydroxy-3,5-dimethylbenzyl)-propanolamine; the structure was determined by X-ray crystallography.     

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 low yield by partial thermal decomposition of 1-{[N,N′-bis(trimethylsilyl)acetamidinium]sulfido}-3-(trimethylsilylamino)-1 H,3 H,1 λ⁵,3 λ⁵-naphtho[1,8 a,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 spectroscopy methods and by X-ray structure analyses.     

Synthesis and structural characterization of mono- and dinuclear NiII and PdII complexes derived from tetradentate 1,7-bis-(pyridin-2-yl)-2,6-diaza-1,6-heptadiene

The reaction of Schiff base 1,7-bis-(pyridin-2-yl)-2,6-diaza-1,6-heptadiene (L) with either NiCl₂·6H₂O or [Pd^IICl₂(CH₃CN)₂]/Na[BF₄] in 1?:?1 stoichiometry yielded mononuclear ionic complexes, trans-[Ni^II(L)(H₂O)₂]Cl₂·3H₂O (1·3H₂O) and [Pd^II(L)][BF₄]₂ (2), respectively; the reaction of L with [Pd^IICl₂(CH₃CN)₂] in 1?:?2 ratio yielded dinuclear cis-[Pd^II ₂(μ-L)Cl₄] (3). Complexes 1–3 were characterized by vibrational spectroscopy and X-ray diffraction; diamagnetic 2 and 3 were also characterized by NMR in solution. The molecular structures of 1 and 2 displayed tetradentate coordination of L with formation of two five-membered and one six-membered chelate rings for both complexes. In 3, L showed bidentate coordination mode for each pyridylimine toward Pd^II. Complex 1 has distorted octahedral geometry around Ni^II and an extended hydrogen-bond network; distorted square planar geometry around Pd^II in 2 and 3 was observed.     

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.     

Synthetic and structural studies of the diiron toluenedithiolate carbonyl complexes with monophosphine ligands

Four diiron toluenedithiolate complexes 2–5 with monophosphine ligands are reported. Treatment of [μ-SC₆H₃(CH₃)S-μ]Fe₂(CO)₆ (1) with tris(3-chlorophenyl)phosphine, tris(4-chlorophenyl)phosphine, tris(4-methylphenyl)phosphine or 2-(diphenylphosphino)benzaldehyde, and Me₃NO?2H₂O in MeCN resulted in the formation of [μ-SC₆H₃(CH₃)S-μ]Fe₂(CO)₅[P(3-C₆H₄Cl)₃] (2), [μ-SC₆H₃(CH₃)S-μ]Fe₂(CO)₅[P(4-C₆H₄Cl)₃] (3), [μ-SC₆H₃(CH₃)S-μ]Fe₂(CO)₅[P(4-C₆H₄CH₃)₃] (4), and [μ-SC₆H₃(CH₃)S-μ]Fe₂(CO)₅[Ph₂P(2-C₆H₄CHO)] (5) in 64–82% yields. Complexes 2–5 have been characterized by elemental analysis, IR, ¹H NMR, ³¹P{¹H} NMR, ¹³C{¹H} NMR and further confirmed by single crystal X-ray diffraction analysis. The molecular structures show that 2–5 contain a butterfly diiron toluenedithiolate cluster coordinated by five terminal carbonyls and an apical monophosphine.     

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.     

Kristallstruktur und Schwingungsspektrum von (H2NPPh3)2[SnCl6]·2CH3CN

Crystal Structure and Vibrational Spectrum of (H₂NPPh₃)₂[SnCl₆]·2CH₃CN Single crystals of (H₂NPPh₃)₂[SnCl₆]·2CH₃CN ( 1 ) were obtained by oxidative addition of tin(II) chloride with N‐chloro‐triphenylphosphanimine in acetonitrile in the presence of water. 1 is characterized by IR and Raman spectroscopy as well as by a single crystal structure determination: Space group , Z = 2, lattice dimensions at 193 K: a = 1029.6(1), b = 1441.0(2), c = 1446.1(2) pm, α = 90.91(1)°, β = 92.21(1)°, γ = 92.98(1)°, R₁ = 0.0332. 1 forms an ionic structure with two different site positions of the [SnCl₆]^2? ions. One of them is surrounded by four N‐hydrogen atoms of four (H₂NPPh₃)⁺ ions, four CH₃CN molecules form N–H···N≡C–CH₃ contacts with the other four N‐hydrogen atoms of the cations. Thus, 1 can be written as [(H₂NPPh₃)₄(CH₃CN)₄(SnCl₆)]²⁺[SnCl₆]^2?.     

Synthesis and characterization of 2-hydroxy-pyridine modified Group 4 alkoxides

The reaction of Group 4 metal alkoxides ([M(OR)₄]) with the potentially bidentate ligand, 2-hydroxy-pyridine (2-HO-(NC₅H₄) or H-PyO), led to the isolation of a family of compounds. The products isolated from the reaction of [M(OR)₄] [where M = Ti, Zr, or Hf; OR = OPrⁱ (OCH(CH₃)₂), OBu^t (OC(CH₃)₃), or ONep (OCH₂C(CH₃)₃] under a variety of stoichiometries with H-PyO were identified by single crystal X-ray diffraction as [(OPrⁱ)₂(PyO-κ²(O,N))Ti(μ-OPrⁱ)]₂ (1), [(ONep)₂Ti(μ(O)-PyO-κ²(O,N))₂(μ-ONep)Ti(ONep)₃] (2), [(ONep)₂Ti(μ(O)-PyO-κ²(O,N))(η¹(N),μ(O)-PyO)(μ-O)Ti(ONep)₂]₂ (2a), [H][(PyO-κ²(O,N))(η¹(O)-PyO)Ti(ONep)₃] (3), [(OR)₂Zr(μ(O)-PyO-κ²(O,N))₂(μ-OR)Zr(OR)₃] (OR = OBu^t (4), ONep (5)), [(OR)₂Zr(μ(O,N)-PyO-κ²(O,N))₂(μ(O,N)-PyO)Zr(OR)₃] (OR = OBu^t (6), ONep (7)), [[(OBu^t)₂Zr(μ(O)-PyO-(κ²(N,O))(μ(O,N)-PyO)₂Zr(OBu^t)](μ₃-O)]₂ (6a), [[(ONep)(PyO-κ²(N,O))Zr(μ(O,N)-PyO-κ²(N,O))₂(μ(O)-PyO-κ²(N,O))Zr(ONep)](μ₃-O)]₂ (7a), [(OBu^t)(PyO-κ²(O,N))Zr(μ(O)-PyO-κ²(O,N))₂((μ(O,N)-PyO)Zr(OBu^t)₃] (8), [(OBu^t)₂Hf(μ(O)-PyO-κ²(N,O))₂(μ-OBu^t)Hf(OBu^t)₃] (9), [(OR)₂ M(μ(O)-PyO-κ²(N,O))₂(μ(O,N)-PyO)M(OR)₃] (OR = OBu^t (10), ONep (11)), and [(ONep)₃Hf(μ-ONep)(η¹(N),μ(O)-PyO)]₂Hf(ONep)₂ (12)·tol. The structural diversity of the binding modes of the PyO led to a number of novel structure types in comparison to other pyridine alkoxy derivatives. The majority of compounds adopt a dinuclear arrangement (1, 2, 4–11) but oxo-based tetra- (2a and 7a), tri- (12), and monomers (3) were observed as well. Compounds 1–12 were further characterized using a variety of analytical techniques including Fourier Transform Infrared Spectroscopy, elemental analysis, and multinuclear NMR spectroscopy.     

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 ruthenium complexes with 1-aryl-imidazole-2-thione

Treatment of [RuCl₂(PPh₃)₃] with 2 equiv. Himt^MPh (Himt^MPh?=?1-(4-methyl-phenyl)-imidazole-2-thione) in the presence of MeONa afforded cis-[Ru(κ ²-S,N-imt^MPh)₂(PPh₃)₂] (1), while interaction of [RuCl₂(PPh₃)₃] and 2 equiv. Himt^MPh in tetrahydrofuran (THF) without base gave [RuCl₂(κ ¹-S-Himt^MPh)₂(PPh₃)₂] (2). Treatment of [RuHCl(CO)(PPh₃)₃] with 1 equiv. Himt^MPh in THF gave [RuHCl(κ ¹-S-Himt^MPh)(CO)(PPh₃)₂] (3), whereas reaction of [RuHCl(CO)(PPh₃)₃] with 1 equiv. of the deprotonated [imt^MPh]^? or [imt^NPh]^? (imt^NPh?=?1-(4-nitro-phenyl)-2-mercaptoimidazolyl) gave [RuH(κ ²-S,N-imt^RPh)(CO)(PPh₃)₂] (R?=?M 4a, R?=?N 4b). The ruthenium hydride complexes 4a and 4b easily convert to their corresponding ruthenium chloride complexes [RuCl(κ ²-S,N-imt^MPh)(CO)(PPh₃)₂] (5a) and [RuCl(κ ²-S,N-imt^NPh)(CO)(PPh₃)₂] (5b), respectively, in refluxing CHCl₃ by chloride substitution of the RuH. Photolysis of 5a in CHCl₃ at room temperature afforded an oxidized product [RuCl₂(κ ²-S,N-imt^MPh)(PPh₃)₂] (6). Reaction of 6 with excess [imt^MPh]^? afforded 1. The molecular structures of 1·EtOH, 3·C₆H₁₄, 4b·0.25CH₃COCH₃, and 6·2CH₂Cl₂ have been determined by single-crystal X-ray crystallography.     

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.     

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.