Gold(I)-triphenylphosphine-arylazoimidazole: Synthesis and spectral (H,C, COSY,HMQC NMR) characterization

The reaction of [Au(OSO₂CF₃)(PPh₃)] with arylazoimidazole in dichloromethane followed by NH₄PF₆ leads to [Au(RAaiR′)(PPh₃)]PF₆ (RAaiR′ = p-R-N=N-C₃H₂-NN-1-R′), abbreviated as N,N′/-chelator, where N (imidazole) and N (azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c), and R′ = Me (I), CH₂CH₃ (II), CH₂Ph (III)]. IR spectra of the complexes show -C=H- and -N=N-stretchings at 1590 and 1370 and at 1100, 755, 695, 545, and 505 cm⁻¹ due to the presence of the triphenylphosphine ring. The ¹H NMR spectral measurements suggest that methylene (-CH₂-) in (RAai)Et gives a complex of the AB type multiplet with a coupling constant of ∼7.6 Hz while in RAaiCH₂Ph it shows AB type quartets with coupling constant of av. 7.2 Hz. Considering the arylazoimidazole moity, there are different carbon atoms in the molecule giving different peaks in the ¹³C NMR spectrum of the complexes. In the ¹H-¹H COSY spectrum of the present complexes, the absence of any off-diagonal peaks extending from δ = 14.12 and 9.55 ppm confirms their assignment of no proton on N(1) and N(3), respectively. Contour peaks in the ¹H-¹³C HMQC spectrum in the present complexes, the absence of any contours at δ = 157.12, 160.76, 155.67, and 157.68–160.2 ppm assign them to the C(2), C(6), C(12), and C(PPh₃) carbon atoms, respectively. The solution structure and stereoretentive transformation in each step have been established from the ¹H NMR results. The article was submitted by the authors in English.     

A novel series of nickel(II)-dppe-arylazoimidazole complexes. Synthesis and spectroscopic characterization

Reaction of [Ni(dppe)Cl₂/Br₂] with AgOTf in CH₂Cl₂ medium following ligand addition leads to [Ni(dppe)(OSO₂CF₃)₂] and then [Ni(dppe)(RaaiR)](OSO₂CF₃)₂ [RaaiR′ = p–R–C₆H₄–N=N–C₃H₂–NN-1–R′,(1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH₂CH₃ (2), CH₂Ph (3), OSO₂CF₃ is the triflate anion]. ³¹P{¹H}-NMR confirm that stable bis-chelated square planar Ni(II) azoimine–dppe complex formation with one sharp peaks. The ¹H NMR spectral measurements suggest azoimine link is present with lot of phenyl protons in the aromatic region. Considering all the moities there are a lot of different carbon atoms in the molecule which gives many different peaks in the ¹³C(¹H)-NMR spectrum. In the ¹H-¹H COSY spectrum in the present complexes and contour peaks in the ¹H-¹³C-HMQC spectrum in the present complexes, assign the solution structure and stereoretentive conformation in each complexes.     

A novel series of gold(III)-bis-triphenylphosphine-arylazoimidazole complexes: synthesis and spectroscopic and redox study

Reaction of [Au(PPh₃)₂(tht)₂](OSO₂CF₃)₃ with RaaiR′ in CH₂Cl₂ medium following ligand addition leads to [Au(PPh₃)₂(RaaiR′)](OTf)₃ [RaaiR′ = p-R–C₆H₄–N=N–C₃H₂–NN–1–R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH₂CH₃ (2), CH₂Ph (3), PPh₃ is triphenylphosphine, OSO₂CF₃ is the triflate anion, tht is tetrahydrothiophen]. The maximum molecular peak of the corresponding molecule is observed in the ESI mass spectrum. The ¹H-nmr spectral measurements suggest methylene, –CH₂–, in RaaiEt gives a complex AB type multiplet while in RaaiCH₂Ph it shows AB type quartets. ¹³C-nmr spectrum suggests the molecular skeleton. In the ¹H–¹H COSY spectrum as well as contour peaks in the ¹H–¹³C heteronuclear multiple-quantum coherence (HMQC) spectrum assign the solution structure. Electrochemistry assign ligand reduction part rather than metal oxidation.     

Palladium(II)-dppe-arylazoimidazole complexes: Synthesis,and spectroscopic characterization

Reaction of [Pd(dppe)Cl₂/Br₂] with AgOTf in a dichloromethane medium followed by ligand addition led to [Pd(dppe)(OSO₂CF₃)₂] and then [Pd(dppe)(RaaiR)](OSO₂CF₃)₂ [RaaiR′ = p-R-C₆H₄-N=N-C₃H₂-NN-1-R′, (1–3), abbreviated as a N,N′-chelator, where N(imidazole) and N(azo) are represented by N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH₂CH₃ (2), CH₂Ph (3), OSO₂CF₃ is the triflate anion, dppe = 1,2-bis-(diphenylphosphinoethane)]. ³¹P “¹H” NMR confirmed that due to the two phosphorus atom interaction in the azoimine symmetrical environment one sharp peak was formed. The ¹H NMR spectral measurements suggest that azo-imine link with lot of phenyl protons in the aromatic region. ¹³C (¹H) NMR spectrum, ¹H, ¹H COSY and ¹H, ¹³C HMQC spectrum assign the solution structure and stereo-retentive conformation in each complex.     

Nickel(II)-dppa-arylazoimidazole complexes: Synthesis and detailed spectroscopic study

The reaction of [Ni(dppa)(Cl)₂] or [Ni(dppa)(Br)₂] with AgOTf gives [Ni(dppa)(OTf)₂], which then form [Ni(dppa)(RaaiR)](OSO₂CF₃)₂ under the action of arylazoimidazole(RaaiR) in a dichloromethane medium [RaaiR′ = p-R-C₆H₄-N=N-C₃H₂-NN-1-R′, (I–III), abbreviated as N,N′-chelating agent, where N(imidazole) and N(azo) represent N and N’, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (I), CH₂CH₃ (II), CH₂Ph (III), OSO₂CF₃ is the triflate anion]. The ¹H NMR spectral measurements suggest that a bound azoimine is responsible for a number of signals of phenyl protons in the aromatic region. The molecules of the complexes contain a number of different carbon atoms which gives a number of different peaks in the ¹³C (¹H) NMR spectrum. The text was submitted by the author in English. The text was submitted by the author in English.     

Multinuclear NMR investigation on organometallic gold(III) pentafluorophenylarylazoimidazole complexes

Reaction of [Au(C₆F₅)(tht)₂Cl](OTf) with RaaiR′ in CH₂Cl₂ medium leads to [Au(C₆F₅)(RaaiR′)Cl](OTf) [RaaiR′ = p-R–C₆H₄–N=N–C₃H₂–NN-1-R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH₂CH₃ (2), CH₂Ph (3), tht is tetrahydrothiophen]. The maximum molecular peak of [Au(C₆F₅)(MeaaiMe)Cl] is observed at m/z 599.51 (100 %) in the FAB mass spectrum. Ir spectra of the complexes show –C=N– and –N=N– stretching near at 1590 and 1370 cm⁻¹ and near at 1510, 955, 800 cm⁻¹ due to the presence of pentafluorophenyl ring. The ¹H-NMR spectral measurements suggest methylene, –CH₂–, in RaaiEt gives a complex AB type multiplet while in RaaiCH₂Ph shows AB type quartets. ¹³C-NMR spectrum of complexes confirm the molecular skeleton. In the ¹H-¹H-COSY spectrum as well as contour peaks in the ¹H-¹³C HMQC spectrum for the present complexes, assign the solution structure and stereoretentive conformation. The electrochemistry gives the ligand reduction peaks.     

Gold(I)-diphenylphosphinomethane–arylazoimidazole: synthesis and multinuclear NMR investigation

Reaction of [Au₂(dppm)Cl₂] with AgOTf in CH₂Cl₂ medium followed ligand addition and leads to [Au₂(dppm)(RaaiR′)](OTf) [RaaiR′ = p-R–C₆H₄–N = N–C₃H₂–NN–1–R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH₂CH₃ (2), CH₂Ph (3), OSO₂CF₃ is the triflate anion, and dppm is the diphenylphosphinomethane-ring]. The ¹H-n.m.r. spectral measurements suggest methylene, –CH₂–, in RaaiEt gives a complex AB type multiplet while in RaaiCH₂Ph it shows AB type quartets with coupling constant of avg. 6 Hz. Considering all the moities there are a lot of different carbon atoms in the molecule which gives a lot of different peaks in the ¹³C-n.m.r spectrum. In the ¹H–¹H-COSY spectrum of the present complexes and contour peaks in the ¹H–¹³C-HMQC spectrum in the present complexes, assign the solution structure and stereoretentive transformation in each step.     

Ruthenium(II)-arylazoimidazole-8-hydroxyquinolinate complexes: Synthesis,spectral study (H,C, COSY,HMQC-NMR) and redox properties

The reaction of [Ru(OH₂)₂(RaaiR′)₂]²⁺ (RaaiR′ = 1-alkyl-2-(arylazo)imidazole, p-R-C₆H₄-N=N-C₃H₂NN(1)-R′, R = H (1), Me (2), Cl (3); R′ = Me (a), Et (b), CH₂Ph (c)) with 8-quinolinol (HQ) in acetone solution followed by the addition of NH₄PF₆ has afforded violet coloured mixed ligand complexes of the composition [Ru(Q)(RaaiR′)₂](PF₆). The maximum molecular peak of 1b is observed at m’z 790 (50%) in the ESI mass spectrum. Ir spectra of the complexes show -C=N- and -N=N- stretching near at 1590 and 1370 cm⁻¹. The ¹H NMR spectral measurements suggest methylene, -CH₂−, in RaaiEt gives a complex AB type while in RaaiCH₂Ph it shows AB type quartets. Considering the arylazoimidazole and oxine moitie there are twenty different carbon atoms in the molecule which gives a total of twenty different peaks in the C¹³ NMR spectrum of complex 1a. In the ¹H-¹H COSY spectrum of the present complexes, absence of any off-diagonal peaks extending from δ = 14.12 and 9.55 ppm confirm their assignment of no proton on N(1) and N(3) respectively. Contour peaks in the ¹H-¹³C HMQC spectrum in the present complexes, the absence of any contours at δ = 157.12, 160.76, 155.67 ppm and 157.68–160.2 ppm assign them to the C(2), C(6), C(g) and C(h), C(i) carbon atoms respectively. The solution structure and stereoretentive transformation in each step have been established from n.m.r. results. Cyclic voltammograme show a Ru(III)/Ru(II) couple at 1.0–1.1 V versus SCE along with three successive ligand reductions.     

单氢钌配合物与水和2,2,2-三氟乙醇的作用机理

利用原位¹H和³¹P NMR对单氢钌配合物TpRu(PPh₃)(CH₃CN)H [Tp＝hydrotris(pyrazolyl)borate]与H₂O和酸性HOCH₂CF₃的反应进行了研究, 结果显示相应的反应产物分别是TpRu(PPh₃)(CH₃CN)(OH) 和TpRu(PPh₃)(CH₃CN)(OCH₂CF₃). 观察到反应过程中Ru-H…HOH和Ru-H…HOCH₂CF₃分子间的氢键作用. 提出了生成TpRu(PPh₃)(CH₃CN)(OH)和TpRu(PPh₃)(CH₃CN)(OCH₂CF₃)的不同作用机理. 在水存在下, TpRu(PPh₃)(CH₃CN)H 与H₂O反应, 经过中间体TpRu(PPh₃)(H₂O)H和TpRu(PPh₃)(OH)(η²-H₂)生成产物TpRu(PPh₃)(CH₃CN)(OH). 而TpRu(PPh₃)(CH₃CN)H与酸性HOCH₂CF₃反应时, 单氢配体被质子化形成中间体[TpRu(PPh₃)(CH₃CN)- (η²-H₂)](OCH₂CF₃), 进而转变成产物TpRu(PPh₃)(CH₃CN)(OCH₂CF₃). TpRu(PPh₃)(CH₃CN)(OCH₂CF₃)与H₂作用, 经中间体TpRu(PPh₃)(HOCH₂CF₃)H生成TpRu(PPh₃)(η²-H₂)H.     

Gold(III)pentafluorophenylarylazoimidazole: Synthesis and spectral (H, C, COSY, HMQC NMR) characterisation

Reaction of [Au^III(C₆F₅)₃(tht)] with RaaiR′ in dichloromethane medium leads to [Au^III(C₆F₅)₃ (RaaiR′)] [RaaiR′=p-R-C₆H₄-N=N-C₃H₂-NN-l-R′, (1-3), R = H (a), Me (b), Cl (c) and R′= Me (1), CH₂CH₃ (2), CH₂Ph (3), tht is tetrahydrothiophen]. The nine new complexes are characterised by ES/MS as well as FAB, IR and multinuclear NMR (¹H,¹³C,¹⁹F) spectroscopic studies. In addition to dimensional NMR studies as¹H,¹H COSY and¹H¹³C HMQC permit complete assignment of the complexes in the solution phase.     

Organometallic gold(I)–nickel(II)–aryldiethynyl (–C≡C(Ar)C≡C–) phosphine complexes: synthesis and multinuclear n.m.r. study

Silver triflate [AgOTf] assisted de-bromination gives [Ni(dppm/dppe/(PPh₃)₂)(OTf)₂], which on reaction with aryldiethynyls and gold(I) phosphines in CH₂Cl₂ medium, by the self assembly technique, leads to [{Ni(dppm/dppe/(PPh₃)₂}{(1,4-AB)Au(PPh₃)}₂] [{Ni₄(dppm/dppe/(PPh₃)₂)₄(1,4AB)₄}] [dppm/dppe = diphenyl phosphino-methane (1), -ethane (2), where OSO₂CF₃ is the triflate anion]. The maximum molecular peak of the corresponding molecule is observed in the ESI mass spectrum. I.r. spectra of the complexes show –C=C– and –C=N–, as well as phosphine stretching. The ¹H-n.m.r. spectra as well as ³¹P(¹H)-n.m.r. suggest solution stereochemistry, proton movement, phosphorus proton interaction. Considering all the moities there are a lot of carbon atoms in the molecule reflected by the ¹³C-n.m.r. spectrum. In the ¹H–¹H-COSY spectrum of the present complexes and contour peaks in the ¹H–¹³C-HMQC spectrum, assign the solution structure and stereo-retentive transformation in each step.     

Gold(I) ‐Nickel(II)‐4,4′‐bpy‐Phosphine Complexes: Synthesis and Multinuclear NMR Study

Silver triflate [AgOTf] assisted de‐bromination gives [Ni(dppm/dppe/(PPh₃)₂) (OTf)₂], which on reaction with 4,4′‐bpy and gold(I) phosphines in dichloromethane medium by the self assemble technique leads to [{(L)Ni}{(4,4‐bpy)Au(PPh₃)}₂](OTf)₄, ( 1,2,3 ) [{(L)Ni(4,4‐bpy)}₄](OTf)₈, ( 4,5,6 ) [L = dppm/dppe/(PPh₃)₂ = diphenyl phosphino‐methane, ‐ethane, bis‐triphenylphosphine, OSO₂CF₃ is the triflate anion]. The maximum molecular peak of the corresponding molecule is observed in the ESI mass spectrum. Ir spectra of the complexes show ‐C=C‐, ‐C=N‐, as well as phosphine stretching. The ¹H NMR spectra as well as ³¹P (¹H)NMR suggest solution stereochemistry, proton movement, and phosphorus proton interaction. Considering all the moieties, there are a lot of carbon atoms in the molecule reflected by the ¹³C NMR spectrum. In the ¹H‐¹H COSY spectrum of the present complexes and contour peaks in the ¹H^?13C HMQC spectrum, we assign the solution structure and stereoretentive transformation in each step.     

Novel bimetallic Ru-Pt and Fe-Pt Complexes [M(C5R5)(L)2(μ,η1:η2-P4{Pt(PPh3)2})]Y: Synthesis, structure, and exchange processes

Novel bimetallic Ru-Pt and Fe-Pt complexes, [M(C₅R₅)(L)₂(η¹-P₄)]Y (M = Ru, Fe; R = H, Me; L = PPh₃, 1/2Dppf (Ph₂P(C₅H₄)Fe(C₅H₄)PPh₂), 1/2Dppe (Ph₂PCH₂CH₂PPh₂); Y = PF₆, CF₃SO₃, BPh₄) were synthesized for the first time by the reaction of η¹-tetraphosphorus complexes of ruthenium(II) and iron(II), [M(C₅R₅)(L)₂(η¹-P₄)]Y with platinum(0) complex [Pt(η²-C₂H₄)(PPh₃)₂] in acetone. The structures and compositions of the title complexes were studied by the ³¹P NMR, correlated ³¹P-³¹P NMR COSY, NOESY, ¹H-spectroscopy, and elemental analysis. The carbene-like fragment Pt(PPh₃)₂ generated in situ was found to be inserted at the P-P bond of the η¹-coordinated tetraphosphorus and migrate between the phosphorus atoms of the obtained ligand μ, η¹: η²-P₄. The exchange process in the novel complexes was investigated. Original Russian Text ? D.N. Akbayeva, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 9, pp. 673–680.     

Preparation and reactivity of metal-containing monomers 53. Synthesis and stability of a cluster monomer (μ-H)Os3(μ-OCNMe2)(CO)9PPh2CH2CH=CH2 in solution

The stability of the complex (μ-H)Os₃(μ-OCNMe₂)(CO)₉PPh₂CH₂CH=CH₂ (1), which contains a free unsaturated functional group in the terminal ligand PPh₂CH₂CH=CH₂, with respect to isomerization, chelation of the ligand, and other transformations in solutions was examined. No transformations of complex1 were observed in the course of synthesis from (μ-H)Os₃(μ-OCNMe₂)(CO)₉NMe₃ or upon heating in solution. Complex1 as well as complexes (μ-H)Os₃(μ-OCNMe₂)(CO)₉PHPh₂ and (μ-H)Os₃(μ-OCNMe₂)(CO)₉PPh₃, which were formed as admixtures, were isolated in the solid state and identified by¹H,¹H-{³¹P}, and¹H-{¹H} NMR, IR, and Raman spectroscopy and mass spectrometry. For Part 52, see Ref. 1. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1455–1460, August, 2000.     

15N NMR Study of Coordinated Amine,Aminocarbyne, and Carboxamido Groups in Triosmium Clusters

The ¹⁵N NMR spectra of the complexes Os₃(CO)₁₀(μ₂-CONHPrⁱ)(μ₂-C? NHR) (1a, R = Pr; 1b, R = CH₂Ph) and Os₃(CO)₉(NH₂Prⁱ)(μ₂-CONHPrⁱ)(μ₂-C? NHR) (2a, R = Pr; 2b, R = CH₂Ph) are studied by using the ¹H detected (inverse) ¹H-¹⁵N correlated spectroscopy. The ¹⁵N chemical shifts and the ¹H-¹⁵N coupling constants fall in characteristic regions for each of the coordinated amine, aminocarbyne, and carboxamido ligands and these values are related to their bonding types. The NMR data are discussed in terms of the influence of the paramagnetic term which is the major factor determining the chemical shifts. A comparison is made to understand the ¹⁵N chemical-shift differences between the coordinated nitrogen-containing ligands and the corresponding free organic molecules.     

Synthesis and crystal structures of new palladium catalysts for the hydromethoxycarbonylation of alkenes

The preparation and structural characterization of dimeric Pd(I)-Pd(I) complex [Pd₂{(PPh₃)(OSO₂CF₃)}₂].CH₂Cl₂ (1) and three palladium center [Pd₃{(PPh₃)(OSO₂CF₃)}₂] (2) and [Pd₃(PPh₃)₄](SO3CF₃)₂ (3) complexes are reported. The complexes exhibit coordination in which the phosphine phenyl ring is used to stabilize Pd(I) centers in (1) and, Pd(I) and Pd(0) centers in (2) and (3) by acting as π electron donors. The complexes were characterized by single crystal X-ray crystallography.     

Trans influences of Cl−, NCO− and NCS− donors on planar NiS2PN(CO), NiS2PN(CS), NiS2PCl and NiS2P2 chromophores: synthesis,NMR spectral and single crystal X-ray structural studies

Planar [Ni(bedtc)(PPh₃)Cl] (1), [Ni(bedtc)(PPh₃)(NCO)] (2), [Ni(bedtc)(PPh₃)(NCS)] (3), [Ni(bedtc)(PPh₃)(CN)] (4) and [Ni(bedtc)(dppe)]ClO₄ (5) (where bedtc = N-benzyl-N-(2-hydroxyethyl)dithiocarbamate anion, PPh₃ = triphenylphosphine and dppe = 1,2-bis((diphenylphosphino)ethane)) were prepared from [Ni(bedtc)₂]. Complexes 1–5 were characterized by elemental analysis, electronic, IR and NMR (¹H, ¹³C, and ³¹P) spectra. Electronic spectra of the complexes show bands corresponding to dz ² → dxy/dx ² ? y ² transitions. The complexes were diamagnetic. IR and ¹³C NMR studies indicate the mesomeric flow of π-electron density from the dithiocarbamate towards the nickel. In ¹H NMR, α-CH₂–and β-CH₂–protons of–CH₂–CH₂–OH were equally deshielded. The deshielding for the coordinated phosphorus signals in ³¹P NMR spectra for all the cases compared with the free phosphine clearly manifests the drift of electron density from the phosphorus toward the metal on complexation. Single crystal X-ray structures of 1–3 indicate that nickel is in a planar environment with short >S₂C–N bond distances. In 2, a rare mode of coordination between nickel and cyanate (NCO^?) through the nitrogen is observed. Significant asymmetry in Ni–S bond distances were observed for 1–3 clearly supporting the trans influences of Cl^?, NCO^? and NCS^?, respectively, over PPh₃.     

Synthesis,Spectra and Electrochemistry of Dinitro-bis-{1-alkyl-2-(arylazo) imidazole} Ruthenium(II). Nitro-nitroso Derivatives and Reactivity of the Electrophilic {Ru-NO}<Superscript>6</Superscript>System

Ag⁺ assisted aquation of blue cis-trans-cis-RuCl₂(RaaiR′)₂ (4–6) leads to the synthesis of solvento species, blue-violet cis-trans-cis-[Ru(OH₂)₂(RaaiR′)₂](ClO₄)₂ [Raai R′=p-R-C₆H₄ N=N–C₃H₂–NN–1–R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), OMe (b), NO₂ (c) and R′ = Me (1/4/7/10), CH₂CH₃ (2/5/8/11), CH₂Ph (3/6/9/12)] that have been reacted with NO₂⁻in warm EtOH resulting in violet dinitro complexes of the type, Ru(NO₂)₂(RaaiR′)₂ (7–9). The nitrite complexes are useful synthons of electrophilic nitrosyls, and on triturating the compounds, (7b–9b) with conc. HClO₄ nitro-nitrosyl derivatives, [Ru(NO₂)(NO)(OMeaaiR′)₂](ClO₄)₂ (10b–12b) are isolated. The solution structure and stereoretentive transformation in each step have been established from ¹H n.m.r. results. All the complexes exhibit strong MLCT transitions in the visible region. They are redox active and display one metal-centred oxidation and successive ligand-based reductions. The redox potentials of Ru(III)/Ru(II) (E_1/2^M) of (10b–12b) are anodically shifted by ∼ ∼0.2 V as compared to those of dinitro precursors, (7b–9b). The ν(NO) >1900 cm⁻¹ strongly suggests the presence of linear Ru–NO bonding. The electrophilic behaviour of metal bound nitrosyl has been proved in one case (12b) by reacting with a bicyclic ketone, camphor, containing an active methylene group and an arylhydrazone with an active methine group, and the heteroleptic tris chelates thus formed have been characterised.     

Darstellung und spektroskopische Charakterisierung der Persulfoniumsalze (CH3)(CF3)SF3+SbF6− und (CH3)(CF3)2SF2+SbF6− und Kristallstruktur von CF3SF2+SbF6−

Preparation and Spectroscopic Characterization of the Persulfonium Salts (CH₃)(CF₃)SF₃⁺SbF₆^? and (CH₃)(CF₃)₂SF₂⁺SbF₆^? and Crystal Structure of CF₃SF₂⁺SbF₆^? [1] . The preparation of the persulfonium salts (CH₃)(CF₃)SF₃⁺SbF₆^? and (CH₃)(CF₃)₂SF₂⁺SbF₆^? by methylation of the sulfuranes CF₃SF₃ and (CF₃)₂SF₂ with CH₃OSO⁺SbF₆^? in liquid SO₂ is reported. The thermolabile compounds are characterized by IR, Raman, ¹H, ¹³C, and ¹⁹F NMR spectroscopy. CF₃SF₂⁺SbF₆^? crystallizes in the space group C2/c with a=16.889(8) Å, b=7.261(4) Å, c=13.416(7) Å, β=91.08° with 8 formula units per unit cell at 167 K. Cations and anions are connected via short SF contacts forming a Ψ-octahedral surrounding of the central S atom which is in close analogy to the already known CF₃SF₂⁺AsF₆^?.     

Magnesium octa(benzo-15-crown-5)phthalocyaninate in the sodium dodecyl sulfate solutions: A study using electron and 1H NMR spectroscopy

The behavior of magnesium octa(benzo-15-crown-5)phthalocyaninate in water medium in the presence of sodium dodecyl sulfate was studied using both electronic and ¹H NMR spectroscopy, including the method of two-dimensional ¹H-¹H correlation NOESY. In the microheterogeneous environment of the CH₃(CH₂)₁₁OSO₃Na solutions at the concentrations of the latter close to the CMC the phthalocyanine is in monomeric form, while at the concentration less than the critical micelle-formation concentration it becomes a dimer or even more aggregated. The results of the NMR spectroscopic investigation indicate that magnesium octa(benzo-15-crown-5)phthalocyaninate preferrably binds to the CH₃(CH₂)₁₁OSO₃Na micelle in the hydrophobic region of the latter.