Synthesis, characterization and solution behaviour of phosphoryl complexes of tin tetrafluoride

The preparation and characterization of a series of octahedral complexes [SnF₄L₂] (L = (Me₂N)₃PO (1), L = (R₂N)₂P(O)F; R = Me (2); Et (3) or L = R₂NP(O)F₂; R = Me (4); Et (5)) are described. These new adducts have been characterised by multinuclear (¹⁹F, ³¹P and ¹¹⁹Sn) NMR, IR spectroscopy and elemental analysis. The NMR data particularly the ¹⁹F NMR spectra showed that the complexes exist in solution as mixtures of cis and trans isomers. The solution behaviour of the complexes studied by variable temperature NMR in the presence of excess ligand indicated that, unlike in the SnCl₄ analogues, the ligand exchange at room temperature is slow for 1–3 and fast only for 4 and 5. The metal–ligand exchange barriers in [SnF₄L₂] and [SnCl₄L₂] systems were estimated and compared. The results indicate that in addition to the difference in the Lewis acidity between SnF₄ and SnCl₄ the nature of the substituents (fluorine atoms) on the phosphorus atom of the ligand can contribute considerably to the lability of the complex obtained.     

SYNTHESIS OF THE FIRST BENZODISELENAGERMOLES AND ONE SPIROBISDISELENAGERMOLE

Abstract

The first examples of compounds R¹R²GeSe₂C₆H₄R³ (R¹,R²=CH³ C₂H₅, C₃H₂, n-C₄H₉, i-C₅H₁₁, Ph, p-CH₃Ph. R³=H, CH₃, OCH₃) were easily obtained (40–80% yield) from electrophilic cleavage of diselenophenylene zirconocenes by dialkyl or diaryl dichlorogermanes. The synthesis of a spirodi-selenagermole was achieved in the same way using germanium tetrachloride. Analytical data, ¹H and ⁷⁷Se NMR. mass spectra are perfectly consistent with the expected structures.     

Synthesis,characterization, and solution behavior of mercury(II) chloride complexes with phosphine tellurides

The reaction of mercury(II) chloride with neutral phosphine telluride ligands (R₃PTe) produced new mercury(II) complexes, HgCl₂(R₃PTe)₂ [R = Me₂N (1), Et₂N (2), C₄H₈N (3), C₅H₁₀N (4) or ^n-Bu (5)]. Attempts to isolate the complex of HgCl₂ with the morpholinyl ligand, (OC₄H₈N)₃PTe, were unsuccessful. Complexes 1–5 have been characterized by elemental analyses, IR, and multinuclear (³¹P, ¹²⁵Te, and ¹⁹⁹Hg) NMR spectroscopy. The solution behavior of the complexes was investigated using variable temperature NMR spectroscopy in the presence of excess ligand and indicated fast ligand exchange on the NMR timescale at room temperature. The metal–ligand exchange barriers in these complexes were estimated to be in the range 8–11 kcal/mol. The results suggest that a slight change in the nature of the substituents on the phosphorus of the ligand can contribute considerably to the lability of the complex obtained. The NMR data are discussed and compared with those obtained for related phosphine chalcogenide systems.     

Synthesis of optically active hydridocarbonyl triosmium clusters with terpene derivatives as ligands. Molecular structure and absolute configuration of a cluster with a bridging dihydroimidazole ligand

Reactions of the triosmium clusters Os₃(CO)₁₁(NCMe) (1) and Os₃(CO)₁₀(NCMe)₂ (2) with terpene derivatives,viz., (1S,3S,4R,6R)-3-(N,N-dimethylamino)-4-amino-3,7,7-trimethylbicyclo [4.1.0]heptane (3). (3bR,4aR)-(3,4,4-trimethyl-3b,4,4a,5-tetrahydrocyclopropa [3,4]cyclopenta[1,2-c]pyrazol-1-yl)acetic acid (4a), and (3bR,4aR)-3-(3,4,4-trimethyl-3b, 4,4a,5-tetrahydrocyclopropa[3,4]cyclopenta[1,2-c]pyrazol-1-yl)propionic acid (4b), were studied. A complex with the terminally coordinated ligand is formed in the first step of the reaction of diamine3 with cluster1. Heating of the resulting complex is accompanied by activation of one of the methyl groups of the ligand to form diastereomers with the bridging tricyclic dihydroimidazole ligand. One of these diastereomers was studied by X-ray diffraction analysis and its absolute configuration was established. Pyrazolycarboxylic acids react with cluster2 as simple organic acids and are coordinated as a bridge at the Os—Os bond through the carboxyl group. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1447–1454, August, 2000.     

Diorganotin Complexes with N(4)-Phenylthiosemicarbazones: Synthesis,Spectroscopic Characterization,and Antibacterial Activity

Abstract

The organotin(IV) complexes, SnPh₂L^a (1), SnMe₂L^a (2), SnBu₂L^a (3), SnPh₂L^b (4), SnMe₂L^b (5), SnPh₂L^c (6), SnMe₂L^c (7), and SnBu₂L^c (8) were obtained by reaction of SnR ₂Cl₂ (R = Ph, Me, and Bu) with 1-(5-bromo-2-hydroxybenzylidene)-4-phenylthiosemicarbazide (H₂L^a), 1-((2-hydroxynaphthalen-1-yl)methylene)-4-phenylthiosemicarbazide (H₂L^b), and 1-(2-hydroxy-3-methoxybenzylidene)-4-phenylthiosemicarbazide (H₂L^c). The synthesized complexes have been investigated by elemental analysis, IR, ¹H NMR, and ¹¹⁹Sn NMR spectroscopy. The data show that the thiosemicarbazone acts as a tridentate dianionic ligand and coordinates via the thiol group, imine nitrogen, and phenolic oxygen. The coordination number of tin is 5. The in vitro antibacterial activities of the ligands and their complexes have been evaluated against Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria and compared with the standard antibacterial drugs.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the following free supplemental files: Additional figures and tables]     

Tin(IV) Tetrachloride Complexes with Bis-(Dialkylamino)phosphoryl Fluoride: A Multinuclear (119Sn, 31P, 19F,and 1H) NMR Characterization in Solution

The two octahedral complexes SnCl₄·2(O)PF(NR₂)₂ (R = Me or Et) were prepared from reaction of SnCl₄ with the ligand (R₂N)₂P(O)F in anhydrous CHCl₃. The new adducts have been characterized by elemental analysis, IR, and multinuclear (¹¹⁹Sn, ³¹P, ¹⁹F, and ¹H) NMR spectroscopy. The NMR data show that the adducts exist in solution as a mixture of cis and trans isomers with markedly different proportions. When compared with previously described hexamethylphosphoramide (HMPA) and trimethylphosphate (TMPA) analogues, our results indicate that the cis isomer is the predominant species in solution. Low temperature ³¹P and ¹¹⁹Sn NMR spectra show that the compounds partially dissociate in dichloromethane.     

Tin(IV) Chloride Complexes of β-Chlorovinyl Aldehydes: A Multinuclear Nmr Characterization in Solution

Abstract

The reaction of SnCl₄ with β-chlorovinyl aldehydes in anhydrous dichloromethane gave a series of octahedral complexes of the general formula SnCl₄·2L (L = aldehyde). The adducts have been characterized in solution using multinuclear (¹H, ¹³C, and ¹¹⁹Sn) NMR and IR spectroscopy. Solution NMR studies show that the complexes undergo rapid ligand dissociation at ambient temperature. Ligand exchange is slowed significantly at low temperature, such that, in most of the complexes, it is possible to identify both the cis and trans isomers with predominance of the cis form. The magnitude of the metal-ligand interaction was estimated on the basis of ¹¹⁹Sn NMR chemical shifts and used to classify the aldehydes studied according to their Lewis basicity.     

Triphenylethanediol-Derived 2-Chloro-1,3,2- dioxaphospholane: Synthesis,Structure, and Reaction with Chiral Alcohols

The reaction of (S)-1,1,2-triphenylethanediol (3) with phosphorus trichloride leads to the diastereoselective formation of (S _C,R _P)-2-chloro-1,3,2-dioxaphospholane (2). Its configuration has been determined by single crystal X-ray diffraction. When reacted with racemic secondary alcohols, diastereomeric phosphites are obtained, which display substantial shift differences in the ³¹P NMR spectra. Thus, chlorodioxaphospholane 2 can serve as derivatizing reagent for chiral secondary alcohols permitting to determine their enantiomeric excess.     

Transformations of the chiral diphosphine rhodium catalyst [(1,5-COD)Rh(—)R,R-DIOP]+CF3SO3– under conditions of hydrogenation

Transformation products of the cationic rhodium complex [(1,5-COD)Rh(—)R,R-DIOP]⁺CF₃SO₃ ^– (1) (COD is cycloocta-1,5-diene and DIOP is (±)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane), which were obtained in its reactions with molecular hydrogen, base (NEt₃), and solvents in the absence of a substrate, were investigated by ¹H and ³¹P NMR spectroscopy. The solvate complexes [(Solv)₂Rh(—)R,R-DIOP]⁺CF₃SO₃ ^–, which were generated from complex 1 in its reaction with molecular hydrogen, underwent destruction of the diphosphine ligand with elimination of benzene and were subjected to oxidation by traces of moisture and oxygen to form the DIOP dioxide complex with Rh^I. In the absence of hydrogen, complex 1 in solutions produced the diphosphine dioxide rhodium(i) complex and mono- and binuclear rhodium(i) solvate complexes. The scheme of deactivation of the complex in the absence of the substrate was proposed. The catalytic activity of the solvate complexes [(ArH)Rh(—)R,R-DIOP]⁺CF₃SO₃ ^–, which contain benzene, p-xylene, and mesitylene in the coordination sphere, was studied in hydrogenation of Z--acetamidocinnamic acid.     

Selected properties of bi- and trinuclear complexes prepared by the reactions of Ru3(CO)12 with β-substituted oxadienes

The reactions of Ru₃(CO)₁₂with 4-phenylbut-3-an-2-ine (1a), 3-phenyl-1-p-tolylprop-2-an-1-ine (1b), and 1,3-diferrocenylprop-2-an-1-ine (1c) afforded the Ru₂(CO)₆(-H)(O=C(R¹)C(H)=C(R²)) (2) and Ru₃(CO)₈(O=C(R¹)C(H)=C(R²))₂(3) complexes. Dissolution of these complexes in CHCl₃or CH₂Cl₂gave rise to the Ru₂(CO)₄(-Cl)₂(O=C(R¹)C(H)=C(R²)) complexes (4). The thermal transformations of complexes 2and 3in the presence of an excess of the ligand yielded the Ru₂O₂(CO)₄(³-OC(R¹)C(H)(CH₂R²)C(R²)C(H)C(R¹))₂(5) and Ru(CO)₂(O=C(R¹)C(H)=C(R²))₂(6) complexes. Analogous complexes were obtained upon more prolonged heating of the starting reaction mixtures. The structures of complexes 4a, 5a, and 6cwere established by X-ray diffraction analysis and confirmed by spectroscopic data.     

Cadmium(II) complexes with phosphine tellurides: synthesis and multinuclear (31P, 125Te,and 113Cd) NMR characterization in solution

New cadmium(II) complexes with phosphine telluride ligands of the type CdX₂(R₃PTe)_n [X?=?ClO₄^?, n?=?4: R?=?n-Bu (1), Me₂?N (2), C₅H₁₀?N (3), C₄H₈?N (4) or OC₄H₈?N (5); X?=?Cl^–, n?=?2: R?=?n-Bu (6), Me₂?N (7), C₅H₁₀?N (8), C₄H₈?N (9) or OC₄H₈?N (10)] have been synthesized and characterized by elemental analyses, IR and multinuclear (³¹P, ¹²⁵Te, and ¹¹³Cd) NMR spectroscopy. In particular, the solution structures of these complexes were confirmed by ¹¹³Cd NMR at low temperature, which displays a quintuplet for each of the perchlorate complexes and a triplet for each of the chloride complexes due to coupling with four and two equivalent phosphorus atoms, respectively, indicating a four-coordinate tetrahedral geometry for the metal center. These multiplet features were further accompanied by one bond Te–Cd couplings, clearly showing that the ligand is coordinated to the metal through tellurium. The results are discussed and compared with those obtained for closely related phosphine chalcogenide analogs.     

S-(N-(Thiocarbamoyl)benzimido)-dithiocarbamidsäureester

Zusammenfassung Die Synthese der Titelverbindungen3 (R ¹=R ²=C₂H₅;n-C₄H₉) durch Reaktionen von N-(N,N-Diethylthiocarbamoyl)-benzimidoylchlorid (2) mit Natriumdialkyldithiocarbamaten (1) in Aceton wird beschrieben. Die niedrigen Ausbeuten (bis 25% d.Th.) sind durch Nebenreaktionen bedingt. Die Strukturen der Verbindungen werden durch IR-,¹H-NMR-,¹³C-NMR-und Massenspektren bestätigt. Nebenreaktionen werden¹³C-NMR-spektroskopisch verfolgt und die Ergebnisse diskutiert.

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S-(N-(thiocarbamoyl)benzimido)dithiocarbamic esters

Summary The synthesis of the title compounds3 (R ¹=R ²=C₂H₅;n-C₄H₉) by reactions of N-(N,N-diethylthiocarbamoyl)benzimidechloride (2) with sodiumdialkyldithiocarbamates (1) in acetone is described. The low yields (<25%) are caused by the occurrence of side reactions. The structures of the compounds were confirmed by IR,¹H and¹³C NMR, and mass spectroscopy. Side reactions were detected by¹³C NMR spectroscopy; the results are discussed.

     

19F,31P,1H NMR and X-ray crystallographic studies of (pentafluorophenyl)3−n (4-pyrazol-1-yl-2,3,5,6-tetrafluorophenyl) n=1,2,3 Phosphines

New phosphines1–3 have been synthetized by reaction of pyrazolate anion with tris(pentafluorophenyl)phosphine and characterized by¹H,³¹P, and¹⁹F NMR studies.¹⁹F NMR spectral data contribute to the evidence for apara-substitution of tetrafluorophenyl rings. The crystal structure of tris(4-pyrazol-1-yl-2,3,5,6-tetrafluorophenyl)phosphine 1 has been determined, proving that the assignment based on spectroscopic data was correct: C₂₇H₉F₁₂N₆P,M _r = 676.37, monoclinic, space group P2_l/c,a=10.754(2) å,b=10.316(2) å,c = 23.598(5) å,=95.36(3),V=2607(1), å³,Z=4,R ₁=0.042, andwR ₂=0.122.     

Mercury(II) cyanide complexes with alkyldiamines: solid-state/solution NMR,computational, and antimicrobial studies

Mercury cyanide complexes of alkyldiamines (1–6), [Hg(L)(CN)₂] (where L?=?en (1,2-diaminoethane), pn (1,3-diaminopropane), N-Me-en, N, N′-Me₂-en, N, N′-Et₂-en, and N, N′-ipr₂-en), have been synthesized and characterized by elemental analysis, IR, ¹³C, and ¹⁵N solution NMR in DMSO-d₆, as well as ¹³C, ¹⁵N, and ¹⁹⁹Hg solid-state NMR spectroscopy. Complexes 1 and 2 have been studied computationally, built and optimized by GAUSSIAN03 using DFT at B3LYP level with LanL2DZ basis set. Binding modes of en and bn (where bn?=?1,4-diaminobutane) toward Hg(CN)₂ are completely different. Complexes with en and pn show chelating binding to Hg(II), while bn behaves as a bridging ligand to form a polymeric structure, [Hg(CN)₂-bn]_∞ [B.A. Al-Maythalony, M. Fettouhi, M.I.M. Wazeer, A.A. Isab. Inorg. Chem. Commun., 12, 540 (2009).]. The solution ¹³C NMR of the complexes demonstrates a slight shift of the ?C≡N (0.9 to 2?ppm) and ?C–NH₂ (0.25 to 6?ppm) carbon resonances, while the other resonances are relatively unaffected. ¹⁵N labeling studies have shown involvement of alkyldiamine ligands in coordination to the metal. The principal components of the ¹³C, ¹⁵N, and ¹⁹⁹Hg shielding tensors have been determined from solid-state NMR data. Antimicrobial activity studies show that the complexes exhibit higher antibacterial activities toward various microorganisms than Hg(CN)₂.     

Tris(dialkylamino)phosphine Chalcogenide Complexes of Tin(IV) Chloride: A Multinuclear (31P, 77Se,and 119Sn) NMR Characterization

Abstract

Four octahedral complexes of the type SnCl₄.2L [L = (R₂N)₃P(E): E = Se; R = Me(1), Et(2) and E = S; R = Me(3), Et(4)] have been studied in solution by multinuclear (³¹P, ⁷⁷Se, and ¹¹⁹Sn) NMR spectroscopy. ³¹P and ⁷⁷Se NMR data were informative of changes associated with complex formation. The solution structure of the complexes was confirmed by their ¹¹⁹Sn NMR spectra that showed two triplet features for each complex, attributed to a mixture of the expected cis and trans isomers. The triplet signal is due to the coupling with two equivalent phosphorus atoms, consistent with an octahedral geometry around the tin center. In addition, density functional theory (DFT)/B3LYP calculations have been carried out to support the interpretations of NMR data. The results are discussed and compared with those reported for related complexes.

GRAPHICAL ABSTRACT      

Organoselenido Complexes of Tungsten

Organometallic tungsten selenido complexes of the type [cpW(CO)₃]₂Se_m; m = 2 (1), 3 (2), 4 (3), can be easily synthesized via insertion of selenium into the alkali-metal tungsten bond of LiWcp(CO)₃ in appropriate ratios and subsequent oxidation of the produced W-selenolates with O₂/SiO₂. In contrast, reactions of K₂Se₆ with [cpW(CO)₃Cl] and 18-crown-6 in DMF lead to a mixture óf [cpW(CO)₃]₂Se₄ (3), the η¹ Se-bonded selenocarbamato complex [cpW(CO)₃SeC(O)NMe₂] (4) and the ionic complex [(18-crown-6)K]⁺[cpW(Se₄)₂]^? (5). The crystal structures of 3 and 4 together with their ⁷⁷Se NMR data are presented.     

Introduction of a phosphorus ylide moiety into [η-(ω-hydroxy)alkenyl]chromium(0) carbene complexes with Ph3PCCO and consecutive Wittig alkenations with 2-alkynals. Part 12: the chemistry of metallacyclic alkenylcarbene complexes

Ketenylidenetriphenylphosphorane, Ph₃PCCO (2), reacts selectively with the ω-hydroxy group of the alkene-carbene complexes (OC)₄CrC(η²-NMeCH₂CHCHCH₂OH)R¹ (1) (R¹=Me: (1a); Ph: (1b)) to give the acyl ylide terminated complexes (OC)₄CrC[(4,5-η²)-NMeCH₂CHCHCH₂O(O)C-CHPPh₃]R¹ (3) (R¹=Me: (3a); Ph: (3b)). Complexes 3 undergo Wittig alkenation reactions with aldehydes such as 2-alkynals, R²-CC-CHO (R²=H, SiMe₃, Ph), to give the corresponding 4Z, 9E-dien-11-ynes (OC)₄CrC[(4,5-η²)-NMeCH₂CHCHCH₂O(O)C-CHCH-CC-R²]R¹ (4-6) (R¹=Me, R²=H, SiMe₃, Ph: (4a-6a); R¹=Ph, R²=H, SiMe₃, Ph: (4b-6b)). All complexes were characterized in solution by one- and two-dimensional NMR spectroscopy (¹H, ¹³C, ²⁹Si, ³¹P, ¹H/¹H COSY, ¹³C/¹H HETCOR, ³¹P/³¹P EXSY).     

The stereochemistry of a nine-membered ring analogue of nefopam,a nonnarcotic analgesic drug

The solid-state structure of a (±)-homonefopam hydrogenfumarate salt having an-O(CH₂)₃N-fragment was determined by single-crystal X-ray diffraction analysis. Homonefopam hydrogenfumarate gave crystals belonging to the monoclinicP2₁/c space group, and at ambient temperaturea=10.220(1),b=18.187(2),c=10.687(2)A,=94.43(1),V=1980.5(5)å³ Z=4,R(F)=0.039,R _w =0.039,R _W (F)=0.025. The¹H NMR spectrum of homonefopam hydrochloride in CD₂Cl₂ solution showed two species (7:1 ratio) at the prototropic shift-nitrogen inversion slow exchange limit. The solution-state major species has the same conformation andtrans-to-phenyl axial N-methyl disposition found in the crystal as evidenced by three antiperiplanar vicinal³ J (HH) coupling constants in the oxytrimethyleneamino fragment and vicinal coupling constants involving theN-H proton. TheR-ratio method was used to estimate 64(2) O-C(3)-C(4)-C(5) and 75(3) C(3)-C(4)-C(5)-N(6) dihedral angles for the major species in CD₂Cl₂ solution in accord with its proposed structure. The finding of C(3)-C(4) bond time-averaged magnitude³ J (HH) values and severe broadening of signals from other minor species protons suggests conformational heterogeneity for the solution-state minor species.     

Cerebrosides fromfomitopsis pinicola (Sw. Ex Fr.) Karst.

Summary A cerebroside fraction was obtained from the fruit bodies offomitopsis pinicola using column chromatography and then separated into six compounds by reversed-phase HPLC. The sugar component of all cerebrosides wasD-glucose. The major fatty acids were 2-hydroxyfatty acids (C₁₄–C₁₈), the long chain base was identified as 9-methyl-C₁₈-4,8-sphingadienine which is widely distributed in fungi and reported to be essential for the fruit-inducing activity of fungi. Based on degradation studies, fast atom bombardment mass spectrometry, and different¹H and¹³C NMR investigations, the structure of the main cerebroside (1) was determined to be (4E,8E,2S,3R,2R)-N-2-hydroxypalmityl-1-O--D-glucopyranosyl-9-methyl-4,8-sphingadienine.

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Cerebroside ausFomitopsis pinicola (Sw. Ex Fr.) Karst.

Zusammenfassung Aus den Fruchtkörpern vonfomitopsis pinicola wurde ein Cerebrosidgemisch erhalten und durch Säulenchromatographie und HPLC in sechs Verbindungen aufgetrennt. Der Zuckerbaustein aller Cerebroside warD-Glucose. Die Fettsäurekomponenten waren 2-Hydroxyfettsäuren mit einer Kettenlänge zwische C₁₄ und C₁₈. Der Basenteil konnte als 9-Methyl-C₁₈-4,8-sphingadienin identifiziert werden. Diese Verbindung ist in Pilzen weit verbreitet und für die Fruchtbildung verantwortlich. Aus Abbaustudien, FAB-MS und verschiedenen¹H- und¹³C-NMR-Messungen wurde die Struktur des Hauptcerebrosids (1) als (4E,8E,2S,3R,2R)-N-2-hydroxypalmityl-1-O--D-glucopyranosyl-9-methyl-4,8-sphingadienin ermittelt.

     

Electron density distributions in substituted 2,3,4,5-tetraphenyl-1-germacyclopenta-2,4-dienes studied by NMR spectroscopy

The signals in the¹³C NMR spectra of 2,3,4,5-tetraphenyl-1-germacyclopenta-2,4-dienes (R¹=R²=H, Me,cyclo-C₃H₅, SiMe₃, SnMe₃, R¹=Me, R²=H, Cl) were completely assigned using 2D NMR spectroscopy. The pattern of the variation of the chemical shifts in the¹³C NMR spectra indicates that the effects of substituents R¹ and R² on the heterocycle and on the phenyl groups are of inductive rather than mesomeric origin and include the direct through-space polarization of bonds (field effect). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1962–1965, November, 1997.