- Synthesis of nanostructured powders and thin films of iron sulfide from molecular precursors
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Iron(iii) xanthate single-source precursors [Fe(S2COR)3] (R = methyl, ethyl, isopropyl and 1-propyl) were used to deposit iron sulfide thin films and nanostructures by two simple, efficient and low-cost methods (spin coating and solid state deposition). The single-crystal X-ray structures of the iron(iii) n-propyl xanthate and iron(iii) iso-propyl xanthate have been determined. Thermogravimetric analysis (TGA) studies of the complexes shows that decomposition of the complexes produces iron sulfide, pyrite or trolite. The crystallinity of iron sulfide thin films and powder samples was studied using X-ray diffraction (XRD), and their morphology was studied by scanning electron microscopy (SEM).
- Almanqur, Laila,Vitorica-Yrezabal, Inigo,Whitehead, George,Lewis, David J.,O'Brien, Paul
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- Electrochemical deposition of highly-conducting metal dithiolene films
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Electrochemical deposition has been used to prepare a thin film of neutral 4′,4-(3-alkyl)-thiophene-5′,5-hydogen-nickel and copper dithiolenes (Ni-C2, Cu-C2). The application of molecular electrodeposition provides a means to solution process molecular semiconductors of poor solubility, which results from the strong intermolecular interaction required for charge transport. Both Ni-C2 and Cu-C2 form continuous thin films that show intense NIR absorptions, extending to 1800 nm and 2000 nm respectively giving evidence for the strong intermolecular interactions in the solid state. Both films are highly conducting and temperature dependence of resistance gave an activation energy of 0.42 eV and 0.072 eV respectively, with the near-metallic behaviour of Cu-C2 attributed to the additional presence of an unpaired electron.
- Allwright, Emily,Silber, Georg,Crain, Jason,Matsushita, Michio M.,Awaga, Kunio,Robertson, Neil
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- Important Phase Control of Indium Sulfide Nanomaterials by Choice of Indium(III) Xanthate Precursor and Thermolysis Temperature
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Four In(III) xanthate complexes, [In(S2COR)3] where R = Me, Et, iPr and sBu, respectively, were synthesized, characterized and subsequently used as single source molecular precursors via a solventless thermolysis route to obtain indium sulfide materials. By choice of precursor and reaction temperature crystalline powders of tetragonal In2S3, cubic In2S3 and cubic In2.77S4 were acquired. The phase identification and purity were conducted through examination of the experimental powder X-ray diffraction patterns relative to the simulated patterns for single X-ray crystal diffraction.
- Masikane, Siphamandla C.,McNaughter, Paul D.,Lewis, David J.,Vitorica-Yrezabal, Inigo,Doyle, Bryan P.,Carleschi, Emanuela,O'Brien, Paul,Revaprasadu, Neerish
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- Potassium isopropyl xanthate (PIX): An ultra-efficient palladium scavenger
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The increasing employment of palladium-catalyzed reactions in the synthesis of active pharmaceutical ingredients (APIs) has created a pressing need for ultra-efficient palladium removal of the resulting metal contaminants. This communication discusses the identification and development of Potassium Isopropyl Xanthate (PIX) as a simple, readily available and ultra-efficient palladium scavenger capable of removing residual palladium from the API to levels less than 1 ppm. In addition, the discovery of a synergistic effect of iodine, in combination with PIX and other palladium scavengers, to enhance palladium removal has further increased the efficiency of the palladium removal process. The PIX and I2 system has been successfully applied to the ceftolozane sulfate 2nd generation manufacturing chemistry to reduce palladium in the API resulting from a late stage palladium-catalyzed coupling reaction to only 0.1 ppm.
- Ren, Hong,Strulson, Christopher A.,Humphrey, Guy,Xiang, Rong,Li, Guangtao,Gauthier, Donald R.,Maloney, Kevin M.
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- Improved synthesis of the high-mobility organic semiconductor dithiophene-tetrathiafulvalene
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Dithiophene-tetrathiafulvalene (DT-TTF) has been shown to be a promising organic semiconductor for organic transistors, since it combines high mobility with processability. A novel synthesis to prepare this material is described here. It involves the coupling of a 1,3-dithiol-2-one. The yield of this route is higher than previously reported yields. Georg Thieme Verlag Stuttgart.
- Crivillers, Nuria,Oxtoby, Neil S.,Mas-Torrent, Marta,Veciana, Jaume,Rovira, Concepcio
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- Correlations between Nuclear Magnetic Resonance Spectra and Crystal Structures. A Carbon-13 Nuclear Magnetic Resonance Study in the Solid State of the Group 15 Xanthates (A=As(III), Sb(III), or Bi(III); R=Me, Et, or Pri)
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The 13C cross-polarisation magic angle spinning (c.p.m.a.s.) n.m.r. spectra of solid (A=As(III) or Sb(III); R=Me, Et, or Pri; A=Bi(III); R=Me or Pri) exhibit systematic features which correlate well with the known crystal structures.In the case of , for which no crystal structure is available, the 13C c.p.m.a.s. n.m.r. spectrum is consistent with this species crystallising as two polymorphs, and their gross structural features are deduced through the correlations of spectra with structures drawn from the preceding eight Group 15 xanthates.The species K(S2COMe) and K(S2COPri) have been studied similarly.
- Hounslow, Andrea M.,Lincoln, Stephen F.,Tiekink, Edward R. T.
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- Synthesis, Spectroscopy, Semi-empirical and Biological Activities of Organotin(IV) Complexes with o-Isopropyl Carbonodithioic Acid
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New organotin(IV) complexes have been synthesized by treating potassium o-isopropyl carbonodithioate with R2SnCl2/R3SnCl in 1:2/1:1 M/L ratio. All complexes have been characterized by IR and NMR (1H, 13C) spectroscopy. IR results shows that ligand acts as bidentate which is also confirmed by semi-empirical study. NMR data reveals four coordinated geometry in solution. Computed positive heat of formation shows that complex 5 is thermodynamically unstable. UV/visible spectroscopy was used to assess the mode of interaction and binding of the complexes with DNA which shows that complex 5 exhibits higher binding constant as compared to complex 3. In protein kinase inhibition assay, compound 3 was found most active, while other biological activities shows that triorganotin(IV) complexes are biologically more active as compared to diorganotin(IV) complexes.
- Javed, Fatima,Ali, Saqib,Shahzadi, Saira,Khalid, Nasir,Tabassum, Saira,Khan, Imran,Sharma, Saroj K.,Qanungo, Kushal
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- The unexpected formation of a triselenide from 4-methyl-5-tri-n-butylstannyl-1,3-dithiol-2-one and selenium dioxide
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When attempting to apply a Riley oxidation to a stannylated precursor instead of the expected aldehyde an acyclic triselenide was obtained in which a Se3 chain replaces the nBu3Sn substituents of two precursors. The reaction was found to be fully reproducible. The product bearing the Se3 moiety and, hence, potentially possessing beneficial biological activity was analyzed comprehensively including X-ray structural characterization and 77Se NMR.
- Schindler, Claudia,Schulzke, Carola
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- On the phase control of CuInS2 nanoparticles from Cu-/In-xanthates
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In this paper we report the synthesis and single-crystal X-ray characterisation of six novel indium(iii) xanthate complexes. These xanthates have been used as an In-source for the synthesis of highly crystalline CuInS2 nanoparticles in conjunction with a Cu(i)-xanthate. In synthesising the nanoparticles we have also demonstrated an ability to control the phase of the material through choice of solvent.
- Al-Shakban, Mundher,Matthews, Peter D.,Zhong, Xiang L.,Vitorica-Yrezabal, Inigo,Raftery, James,Lewis, David J.,O'Brien, Paul
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- Crystal and molecular structure of tris-(O-isopropylxanthato)-chromium(III)
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The title compound has been synthesized by the reaction of CrCl3*6H2O with K in a 1:3 molar ratio in an aqueous medium.It has been characterized by elemental analysis and IR spectral studies.Crystals of Cr3 are monoclinic, space group P21/n with a = 10.002(2), b = 10.973(1), c = 18.961(6) Angstroem, β = 91.78(2) deg, V = 2079.9 Angstroem3, Z = 4, Dcalc = 1.46 g cm-3, monochromatic radiation (Mo-Kα), λ = 0.71069 Angstroem, μ = 11.2 cm-1, F(0 0 0) = 948, T = 295 K, final R = 0.0320 for 2641 reflections.The environment of the chromium atom is based on an octahedral geometry having six sulfur donor atoms from three symmetrically chelated ligands with average distances: Cr-S = 2.396(9) Angstroem, C-S = 1.690(3) Angstroem and C-O = 1.315(3) Angstroem.The bond distance between oxygen atom and the carbon atom of the isopropyl group (O-Cav = 1.478(4) Angstroem) suggests that the form -S2(-)C = O(+)CH(CH3)2 contributes significantly to the structure of the isopropyl group.
- Bhargava, Sanjeev,Bohra, Rakesh,Mehrotra, R. C.
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- Tripodal pyrrolotetrathiafulvalene receptors for recognition of electron-deficient molecular guests
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We report the synthesis of tripodal receptors with monopyrrolo- tetrathiafulvalene arms 1a,b, based on 1,3,5-substituted 2,4,6-triethylbenzene scaffold. The three converging pyrrolotetrathiafulvalene groups form an electron rich cone-shaped binding site. Molecular hosts 1a,b are capable of binding neutral electron deficient guests in solution, as well as positively charged pyridinium species in the gas phase.
- Watat, Michèle-Laure Lieunang,Dülcks, Thomas,Kemken, Dorit,Azov, Vladimir A.
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- [1,3]-Dithiolo-[4,5-d ][1,3-dithiole]-2,5-dione
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A safe, three-step reaction sequence to [1,3]-dithiolo-[4,5- d ][1,3-dithiole]-2,5-dione starting from carbon disulfide is presented. Optimized reaction conditions, rigorous purification, and full characterization of all intermediates provide reproducibly a final product of superior quality with a melting point of 181 °C (dec.).
- Bourcet, Léa,Müller, Harald
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- Lower-Rim-Modified Calix[4]arene-Pyrrolotetrathiafulvalene Molecular Tweezers
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An approach for the lower rim modification of the calix[4]arene-based molecular tweezes with monopyrrolo-tetrathiafulvalene (MPTTF) arms attached to the upper rim of calixarenes is described. First, calixarene-MPTTF conjugates with free hydroxyl on the lower rim are synthesized using the Ullmann reaction, then hydroxyl groups are substituted by propargyl groups, which can be used for further modification by the click reaction. The new calixarene-TTF derivatives displayed reversible redox processes, as well as demonstrated binding affinity for electron-deficient molecular guests such as tetracyanoquinodimethane. The described synthetic approach will be used for the modular synthesis of molecular receptors tailored for specific applications.
- Azov, Vladimir A.,Korsching, Kai R.,Schlüter, Dirk
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supporting information
p. 4469 - 4476
(2021/08/30)
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- Accessing γ-Ga2S3 by solventless thermolysis of gallium xanthates: A low-temperature limit for crystalline products
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Alkyl-xanthato gallium(iii) complexes of the form [Ga(S2COR)3], where R = Me (1), Et (2), iPr (3), nPr (4), nBu (5), sBu (6) and iBu (7), have been synthesized and fully characterised. The crystal structures for 1 and 3-7 have been solved and examined to elucidate if these structures are related to their decomposition. Thermogravimetric analysis was used to gain insight into the decomposition temperatures for each complex. Unlike previously explored metal xanthate complexes which break down at low temperatures (2S3 was the sole product formed. In the case of R = Me, Chugaev elimination did not occur and amorphous GaxSy products were formed. We conclude therefore that the low-temperature synthesis route offered by the thermal decomposition of metal xanthate precursors, which has been reported for many metal sulfide systems prior to this, may not be appropriate in the case of gallium sulfides.
- Alderhami, Suliman A.,Collison, David,Lewis, David J.,McNaughter, Paul D.,O'Brien, Paul,Spencer, Ben F.,Vitorica-Yrezabal, Inigo,Whitehead, George
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p. 15605 - 15612
(2019/11/03)
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- Copper-catalyzed synthesis of thiazol-2-yl ethers from oxime acetates and xanthates under redox-neutral conditions
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A novel copper-catalyzed annulation of oxime acetates and xanthates for the synthesis of thiazol-2-yl ethers with remarkable regioselectivity has been developed. Various oxime acetates, whether derived from aryl ketones or alkyl ketones, or natural product cores are suitable for this conversion. Unique dihydrothiazoles were also obtained when both reaction sites were methine. Mechanistic studies indicated that imino copper(iii) intermediates were involved. In addition, this protocol proceeded under redox-neutral conditions and did not require additives or ligands.
- Zhu, Zhongzhi,Tang, Xiaodong,Cen, Jinghe,Li, Jianxiao,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 3767 - 3770
(2018/04/17)
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- Syntheses, structures, and electrochemical studies of N,N′-bis(alkylthiocarbamate)butane-2,3-diimine Cu(II) complexes as pendent alkoxy derivatives of Cu(ATSM)
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A series of N2S2-Cu(II) complexes based on N,N′-bis(alkylthiocarbamate)butane-2,3-diimine ligands have been synthesized and characterized by spectroscopic, electrochemical, and single crystal X-ray diffraction methods. This class of ligands contains a conjugated N2S2chelate framework with a non-coordinating, terminal alkoxy (–OR) group. Ligands and Cu(II) complexes were investigated for R = Me, Et,nPr,iPr, and octyl. Additionally, N,N′-bis(ethylthiocarbamate)hexane-3,4-diimine and its Cu(II) complex were analyzed. Single crystal X-ray diffraction studies on all six Cu(II) complexes confirm a square planar Cu(II) environment with no significant changes in the core structure as a function of R. Spectroscopic studies are consistent with a similar electronic environment in all complexes. However, electrochemical investigations reveal significant shifts in the CuII/Iand CuIII/IIreduction potentials throughout the series. The complexes are analogues of the well-known bis(thiosemicarbazone) Cu(II) which contain a similar donor core with terminal, non-coordinating amines. Substitution of the terminal amines of bis(thiosemicarbazones) with the alkoxy groups of N,N′-bis(alkylthiocarbamate)butane-2,3-diimines allows tuning of redox potentials with minimal changes in the physical and electronic structure.
- Vishnosky, Nicholas S.,Mashuta, Mark S.,Buchanan, Robert M.,Grapperhaus, Craig A.
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- Tuning of tetrathiafulvalene properties: Versatile synthesis of N-arylated monopyrrolotetrathiafulvalenes via Ullmann-type coupling reactions
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An Ullmann-type coupling reaction was employed for the preparation of several N-arylated monopyrrolotetrathiafulvalenes with variable substitution patterns. Spectroscopic and electrochemical properties of the coupling products strongly depend on the electronic nature of the aromatic substituents due to their direct conjugation with the tetrathiafulvalene chromophore. The crystal packing of the arylated monopyrrolotetrathiafulvalenes is primarily defined by networks of C-H...X weak hydrogen bonds and short S...S contacts involving the tetrathiafulvalene moieties.
- Azov, Vladimir A.,Janott, Diana,Schlüter, Dirk,Zeller, Matthias
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supporting information
p. 860 - 868
(2015/08/18)
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- A structural and spectroscopic investigation of octahedral platinum bis(dithiolene)phosphine complexes: Platinum dithiolene internal redox chemistry induced by phosphine association
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The complexes [Pt(mdt)2] (4; mdt = methyldithiolene, [Me 2C2S2]n-), [Pt(adt)2] (5; adt = p-anisyldithiolene, [(MeO-p-C6H4)2C 2S2]n-), and [Pd(adt)2] (10) have been prepared in yields of >90% via transmetalation reactions with the corresponding [R2Sn(S2C2R′2)] complexes (R = nBu, R′ = Me; R = Me, R′ = -C 6H4-p-OMe, 3). Intraligand C-S and C-Cchelate bond lengths (~1.71 and ~1.40 A, respectively) obtained by X-ray crystallography show these compounds to be comprised of radical monoanions mdt?- and adt?-. The six-coordinate octahedral adducts [Pt(adt)2(dppe)] [6; dppe = 1,2-bis(diphenylphosphino)ethane] , trans-[Pt(adt)2(PMe3)2] (8), and trans-[Pt(mdt)2(PMe3)2] (9) have also been prepared, and crystal structures reveal dithiolene ligands that are fully reduced ene-1,2-dithiolates (C-S and C-Cchelate = ~1.77 and 1.35 A, respectively). Reduction of the dithiolene ligand thus occurs to accommodate the +IV oxidation state typical of octahedral six-coordinate platinum. The cyclic voltammogram of 5 shows two fully reversible reductions at -0.11 and -0.84 V in CH2Cl2 (vs Ag/AgCl), attributed to successive (adt?- + e- → adt2-) processes, and a reversible oxidation at +1.01 V. The cyclic voltammogram of 9 shows two reversible oxidations at +0.38 and +0.86 V, which are assigned as successive (adt2- → adt?- + e-) oxidations. Consistent with their formulation as having fully reduced dithiolene ligands, the UV-vis spectra for 6, 8, and 9 show no low-energy absorptions below 700 nm, and the S K-edge XAS spectra of 6 and 8 show dithiolene sulfur that is reduced relative to that in 5. The introduction of PMe3 to 10 did not produce the palladium analogue of 8 but rather [Pd(adt)(PMe 3)2] (11). The reaction of [PdCl2(PPh 3)2] with Li2(mdt) produced a mixture of [Pd(mdt)(PPh3)2] (12, 20%) and [(Ph3P)Pd(μ- 1,2-mdt-S,S′:S)2Pd(PPh3)] (13, 28%), with the latter having C2 symmetry with a Pd2S2 core structure folded along the S···S axis.
- Chandrasekaran,Greene, Angelique F.,Lillich, Karen,Capone, Stephen,Mague, Joel T.,Debeer, Serena,Donahue, James P.
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p. 9192 - 9205
(2014/12/09)
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- Synthesis and characterization of various xanthates and their effects on germination and early seedling growth in wheat (Triticum aestivum L.)
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Potassium n-propyl xanthate potassium iso-propyl xanthate, potassium n-butyl xanthate and potassium iso-butyl xanthate were synthesized and characterized by melting point, elemental analysis and infrared spectra and their effect on germination and early seedling growth in wheat (Triticum aestivum L.) were studied. All chemical treatments decreased per cent germination length and dry weight of shoots decreased at all concentrations except at 5 and 10 ppm n-propyl xanthate. Root length also decreased except at 5,10 and 25 ppm of potassium iso-propyl xanthate and potassium iso-butyl xanthate, root dry weight decreased with all chemical treatments except at 5 and 10 ppm in case of potassium n-butyl xanthate.
- Rani, Alka,Gupta
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p. 6995 - 6996
(2013/07/26)
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- An expeditious microwave-assisted synthesis of mercapto benzazoles, quinazolinone and oxadiazoles
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A simple, convenient and high yielding synthetic method for the preparation of various mercapto derivatives of benzimidazoles 2a-e, benzoxazole 2f, benzothiazole 2g, quinazolinone 2h, 5- substituted-1,3,4-oxadiazoles 4a-f by the treatment of a series of O, S and N heteroatoms containing bifunctional molecules with potassium isopropyldithiocarbonate under microwave irradiation technique is described.
- Mahesh Kumar,Dubey
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p. 1619 - 1622
(2013/01/15)
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- Synthesis and Characterization of Bis(xanthate) Complexes of Mo(II) and W(II). Crystal Structure of
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The reactions of with potassium xanthates, K(S2COR), give the red crystalline compounds t (4) in which the xanthate groups seem to act as ν3-(S,S',C) pseudo-allylic ligands.Formation of the dicarbonyl species is not detected, but the isopropyl derivative (5) can be obtained by carbonylation of (3) under relatively forcing conditions.The tungsten complex reacts similary with K(S2COR) but gives mixtures of (n=1 or 2).The monophosphine derivatives exhibit n.m.r. spectroscopic features similar to those of (1)--(5), but for the bis(phosphine) species a formulation containing uni- and bi-dentaxe xanthate groups, is proposed, aand this has been confirmed by an X-ray crystal structure determination of complex (9). Formation of the dithiocarbonate complexes, during the reactions leading to the above xanthates has also been observed.Complex (9) istriclinic, space group P1, with unit-cell constants a=8.775(2), b=14.027(5), c=11.806(5) angstroem,α=106.09(2), β=75.74(3), γ=109.06(4)deg, and Z=2.The structure was refined to an R value of 0.032 by using 2878 independent observed refrections.
- Carmona, Ernesto,Contreras, Leopoldo,Sanches, Luis J.,Gutierrez-Puebla, Enrique,Monge, Angeles
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p. 2003 - 2010
(2007/10/02)
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- The conversion of Alcohols into Xanthates in Organic Media. II. Kinetics and Thermochemictry of the Conversion of Isopropyl Alcohol into a Xanthate under Adiabatic Conditions
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The kinetics of the conversion of isopropyl alcohol into a xanthate have been investigated by the continuous flow method for an equimolar reactant ratio under adiabatic conditions.It is shown, that the reaction is described by the kinetic first-order equation.The kinetic and thermochemical characteristics of the reaction have been determined by analysing the results on a computer.
- Savel'yanov, V. P.,Utrobin, N. P.,Savel'yanova, R. T.,Evseev, N. N.
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p. 720 - 721
(2007/10/02)
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- The Conversion of Alcohols into Xanthates in Organic Media I. The Conversion of Isopropyl Alcohol into a Xanthate under Isothermal Conditions
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The kinetics of the reaction of potassium isopropoxide with carbon disulphide in absolute isopropyl alcohol have been investigated by the continuous flow method in the range 18 - 38 deg C.The reaction obeys a second-order kinetic equation, the process being of first order with respect to the isopropoxide and carbon disulphide.The activation parameters, the heat of reaction and the heat of solution of potassium isopropylxanthate in isopropyl alcohol have been determined.
- Savel'yanova, R. T.,Utrobin, N. P.,Savel'yanov, V. P.,Evseev, N. N.
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p. 718 - 719
(2007/10/02)
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