The methylation of inorganic tin by humic materials in an aquatic environment

This paper presents a study of methylation of inorganic tin (SnCl₄·5H₂O) by humic materials (humic and fulvic acids) isolated from the sediment of Tianjin Harbor, Tianjin, China, and the effects of pH, salinity, and the concentration of inorganic tin on the production of methyltin were investigated. These humic materials could methylate inorganic tin, and the methyltin product was mainly monomethyltin. Low molecular weight compounds of the humus fraction (i.e. fulvic acid) were more active in the methylation, which could be facilitated by salinity and affected by pH.     

Kinetic studies of the interaction between organotin(IV)chlorides and tetraaza Schiff bases: Synthesis and characterization of some novel tin(IV) Schiff base complexes

In this article the kinetics of the interaction between the teteraaza Schiff bases as donor with organotin(IV)chlorides as acceptor was studied in acetonitrile. Teteraaza Schiff bases are (Me₄‐Bzo₂[14]tetraeneN₄) (tmtaa), (Me₄‐4‐CH₃Bzo₂[14]tetraeneN₄) (Metmtaa), (Me₄‐4‐ClBzo₂[14]tetraeneN₄) (Cltmtaa), i.e., [(Me₄‐Bzo₂[14]tetraeneN₄)] means that (5,7,12,14‐tetramethyldibenzo[b,i][1,4,8,11] tetraazacyclotetradecine) (tmtaa) and organotin(IV)chlorides are methyltin(IV) trichloride, phenyltin(IV)trichloride, dimethyltin (IV)dichloride, diphenyltin(IV) dichloride, and dibutyltin(IV)dichloride. The kinetic parameters and the second‐order k₂ rate constants show the donor properties of tetraaza Schiff bases as Me₄‐4‐CH₃Bzo₂[14]tetraeneN₄ > Me₄‐Bzo₂[14]tetraeneN₄ > Me₄‐4‐ClBzo₂[14]tetraeneN₄ and also the acceptor properties of organotin(IV)chlorides as PhSnCl₃ > MeSnCl₃ > Ph₂SnCl₂ > Me₂SnCl₂ > Bu₂SnCl₂. An excellent linearity of k_obs vs. the molar concentration of the acceptor, the high span of k₂ values, the large negative values of ΔS^≠, and the low ΔH^≠ values suggest an associative (A) mechanism for the acceptor–donor interaction. © 2011 Wiley Peiodicals, Inc. Int J Chem Kinet 43: 247–254, 2011     

Preparation of di(n-butyl) tin and di(n-octyl) tin dihalides by the direct synthesis method

The direct synthesis of the two industrially important organotin intermediates, di(n-butyl)tin and di(n-octyl)tin dihalides, has been investigated by reacting the appropriate alkyl halide with metallic tin undervarying conditions. Observations were made on the influences of temperature, pressure, reaction time, nature of the tin metal, organic halide/tin reactant ratios and the presence of catalysts on the extent of tin conversion and yields of the organotin products. The efficacy of the onium halides, notably n-Bu₄NI, Me₃SI and Ph₃MeAsI, either singly or in binary combinations with iodine or inorganic iodine compounds, in catalysing the synthesis of the above dialkyltins as well as higher di(n-alkyl)tin analogues is described.     

Synthesis,Spectral, and 3D Molecular Modeling of Tin(II) and Organotin(IV) Complexes of Biologically Active Schiff Bases Having Nitrogen and Sulfur Donor Ligands

Reaction of tin(II) chloride and dimethyltin dichloride with Schiff bases derived from S-benzyldithiocarbazate leads to the formation of a new series of tin(II) and organotin(IV) complexes of general formula SnCl ₂ .L and Me ₂ SnCl ₂ .L (where L = Schiff bases are derived from the condensation of S-benzyldithiocarbazate with heterocyclic aldehydes). An attempt has been made to prove the structures of the resulting complexes on the basis of elemental analysis, conductance measurements, molecular weight determinations, infrared, and multinuclear magnetic resonance ( ¹ H, ¹³ C, and ¹¹⁹ Sn NMR) spectral studies. A few representative ligands and their tin complexes have also been screened for their antibacterial and antifungal activities and found to be quite active in this respect.     

Speciation and determination of tin(IV) and organotin compounds in sea-water by hydride generation-atomic-absorption spectrometry with an electrically heated long absorption cell

A method is described for the determination of nanogram or subnanogram amounts of Sn(IV) and the halides of methyltin, dimethyltin, trimethyltin, n-butyltin, dibutyltin, and tributyltin. These compounds are volatilized from water samples by hydride generation, collected on a chromatographic stationary phase, desorbed in order of increasing boiling point, and detected by atomic-absorption spectrometry with atomization in a long electrothermally heated alumina tube furnace. The absolute detection limits are in the range 0.4-1.5 ng with a reproducibility of 4-15% for inorganic tin and organotin compounds.     

Can mono- or di-butyltin chlorides produce tributyltin chloride at elevated temperatures? Implications for applications in chemical vapour deposition

The thermolysis of the butyltin chlorides at 200-300 °C in the liquid phase has been investigated by ¹H, ¹³C, and ¹¹⁹Sn NMR spectroscopy. The stabilities follow the order: Bu₂SnCl₂ > Bu₃SnCl > BuSnCl₃. Only tributyltin chloride showed any evidence of redistribution, giving dibutyltin dichloride, together with metallic tin, butane, and but-1-ene, which would be formed by decomposition of tetrabutyltin. Dibutyltin dichloride decomposed to give mainly butane with no other apparent liquid organotin compound. Butyltin trichloride gave butane, some butene, and metallic tin, and showed no evidence of forming tributyltin chloride by the redistribution reaction, which would have environmental implications for its use in the CVD coating of glass.     

[C5H12N]SnCl3: A Tin Halide Organic–Inorganic Hybrid as an Above-Room-Temperature Solid-State Nonlinear Optical Switch

Nonlinear optical (NLO) switches driven by a solid-state structural phase transition have attracted extensive attention; however, above-room-temperature solid-state NLO switch materials are still sparse. Herein, we report an above-room-temperature tin halide organic–inorganic hybrid quadratic NLO switchable material, N-methylpyrrolidinium trichloride stannite ([C₅H₁₂N]SnCl₃, MPSC). The MPSC crystal exhibits a phase-matchable NLO property that is 1.1 times that of KH₂PO₄ (KDP) and NLO switching behavior, changing from a high second harmonic generation (SHG) response to a low SHG response at 383 K, thereby demonstrating its prospective applications in the field of nonlinear optics. Variable-temperature crystal structural analysis combined with theoretical calculations revealed that the large NLO response stems from the inorganic SnCl₃ moiety, whereas the high-performance NLO switching properties mainly originate from the order/disorder transformation of the N-methylpyrrolidinium. This work provides a new approach to designing and exploring new high-performance quadratic NLO switches involving tin halide organic–inorganic hybrids.     

Structure and properties of double‐C,N‐chelated tri‐ and diorganotin(IV) halides

Tri‐ and di‐organotin(IV) compounds containing one or two 2‐(dimethylaminomethyl)phenyl‐ (L^CN) groups as chelating ligands were prepared by reactions of lithium compound L^CNLi with an appropriate amount of (organo)tin halide. The geometry of tin in 1 ((L^CN)₂SnPhCl) is on the boundary between octahedral and trigonal bipyramidal. The diorganotin compounds 2–4 ((L^CN)₂SnX₂, where X = Cl, Br, I) have a distorted octahedral geometry in the solid state and show dynamic processes in solution with a lowering of activation energy of the dynamic process going from diiodide to dichloride derivative. Compound 5 (L^CNSnPhCl₂) has a trigonal bipyramidal structure with non‐equivalent chlorine atoms. Copyright © 2005 John Wiley & Sons, Ltd.     

A novel mode of access to polyfunctional organotin compounds and their reactivity in Stille cross-coupling reaction

Mono-, di-, tri- and tetra-functional organotin compounds were easily prepared in a sonicated Barbier reaction using ultrasound technology via coupling reaction of organo halides with tin halides (Bu₃SnCl, Bu₂SnCl₂, BuSnCl₃, SnCl₄) mediated by magnesium metal. The di- and tri-functional organotin compounds were tested in a Stille cross-coupling reaction in order to ascertain how many groups were transferred.     

Formation of Platinum–Tin Bond by Tin(II)Chloride Insertion

The first ¹¹⁹Sn NMR evidence for the presence of direct platinum–tin bond in solution has been obtained for PtCl(SnCl₃)(bdpp) complex (bdpp = (2S,4S)-2,4-bis(diphenylphosphino)pentane). Various PtCl₂(L₂) complexes (L₂ = heterobidentate P–P, P–O, P–N, P–S chelating ligands) have been reacted with tin(II)chloride resulting in the formation of the corresponding PtCl(SnCl₃)(L₂) derivatives. Tin(II)chloride has been inserted into the Pt–Cl bond transto the harder donor atom of the L₂ ligand.     

Synthesis,spectroscopic characterization (IR, 1H, 13C and 119Sn NMR,electrospray mass spectrometry) and toxicity of new organotin(IV) complexes with N,N′,O‐ and N,N′,S‐scorpionate ligands

New organotin(IV) derivatives containing the anionic ligands bis(3,5‐dimethylpyrazol‐1‐yl)dithioacetate [LCS₂]⁻ and bis(3,5‐dimethylpyrazol‐1‐yl)acetate [LCO₂]⁻ have been synthesized from reaction between (CH₃)₂SnCl₂ and lithium salts of the ligands. Mononuclear complexes of the type {[LCX₂](CH₃)₂SnCl} (X = S or O) have been obtained and fully characterized by elemental analyses and FT‐IR in the solid state and by NMR (¹H, ¹³C and ¹¹⁹Sn) spectroscopy, conductivity measurements and electrospray ionization mass spectrometry in solution. The acute toxicity of new organotin(IV) derivatives on rat was studied, comparing their effect with those of dimethyltin chloride (CH₃)₂SnCl₂. The comparison of LD₅₀ of organotin(IV) complexes and (CH₃)₂SnCl₂ administered intraperitoneally, as a single dose, evaluated in vivo on rats, showed that toxicity decreases as follows: (CH₃)₂SnCl₂ > LCO₂ > LCS₂. The effect of these organotin(IV) complexes on DNA was evaluated in vitro and in vivo on rats treated with different doses of these compounds (1/20 LD₅₀ and 1/100 LD₅₀). The lymphocyte DNA status was assessed by the comet assay, a rapid and sensitive single‐cell electrophoresis technique, used to detect primary DNA damage in individual cells. After 36 h from the start of treatment the two new organotin(IV) derivatives induced a significant rise in comet assay parameters, indicating an increasing presence of damaged DNA. Copyright © 2005 John Wiley & Sons, Ltd.     

On the reaction of tin dichloride and of metallic tin with hydrochloric acid in the presence of alkenes. The question of trichlorostannane(IV) or chlorostannate(II) intermediates.

Studies of the reaction of tin dichloride and of metallic tin with hydrochloric acid gas in diethyl ether are described. On the basis of spectroscopic and analytical data it is concluded that the product is not to be regarded as a tin-hydrogen bonded analog of chloroform, viz. trichlorostannane(IV), and the formation of an equilibrium mixture of hydrogen trichlorostannate(II) and dihydrogen tetrachlorostannate(II) is tentatively suggested. The complexes slowly decompose as a result of diethyl ether cleavage, yielding ethanol and ethyl chloride, together with traces of ethyltin trichloride.The mechanism of addition of the complexes to methyl acrylate is discussed in terms of a 1,4-addition involving initial protonation of oxygen. Reaction of the resulting β-carbomethoxyethyltin trichloride with tin or with zinc gives rise to mixtures of bis(β-carbomethoxyethyl)tin dichloride and tris(β-carbomethoxyethyl)tin chloride Similar reactions were observed for the first time with methyltin trichloride, the reaction with zinc being extremely fast at room temperature.     

The use of sodium tetraethylborate in the derivatization of octyltin compounds

Octyltin trichloride (OctSnCl₃) and dioctyltin dichloride (Oct₂SnCl₂) have been reacted with sodium tetraethylborate (NaBEt₄) to yield the volatile tetraalkyltin derivatives OctSnEt₃ and Oct₂SnEt₂. Single and mixed solutions of the octyltin chlorides have been derivatized, separated and quantified using interfaced GC AA and GC MS methodology.     

Isostructural crystal packing and hydrogen bonding in alkyl­ammonium tin(IV) chloride compounds

The three isostructural compounds butyl­ammonium hexa­chlorido­tin(IV), pentyl­ammonium hexa­chlorido­tin(IV) and hexyl­ammonium hexa­chlorido­tin(IV), (C_nH_2n+1NH₃)₂[SnCl₆], with n = 4, 5 and 6, respectively, crystallize as inorganic–organic hybrids. As such, the structures consist of layers of [SnCl₆]²⁻ octa­hedra, separated by hydro­carbon layers of inter­digitated butyl­ammonium, pentyl­ammonium or hexyl­ammonium cations. Corrugated layers of cations alternate with tin(IV) chloride layers. The asymmetric unit in each compound consists of an anionic component comprising one Sn and two Cl atoms on a mirror plane, and two Cl atoms in general positions; the two cations lie on another mirror plane. Application of the mirror symmetry generates octa­hedral coordination around the Sn atom. All compounds exhibit bifurcated and simple hydrogen‐bonding inter­actions between the ammonium groups and the Cl atoms, with little variation in the hydrogen‐bonding geometries.     

Organotin–Oxido Cluster‐Based Multiferrocenyl Complexes Obtained by Hydrolysis of Ferrocenyl‐Functionalized Organotin Chlorides

Three organotin–oxido clusters were formed by hydrolysis of ferrocenyl‐functionalized organotin chloride precursors in the presence of NaEPh (E=S, Se). [R^FcSnCl₃?HCl] ( C ; R^Fc = CMe₂CH₂C(Me)?N?N?C(Me)Fc) and [SnCl₆]^2? formed {(R^FcSnCl₂)₃[Sn(OH)₆]}[SnCl₃] ( 3 a ) and {(R^FcSnCl₂)₃[Sn(OH)₆]}[PhSeO₃] ( 3 b ), bearing an unprecedented [Sn₄O₆] unit, in a one‐pot synthesis or stepwise through [(R^FcSnCl₂)₂Se] ( 1 ) plus [(R^FcSnCl₂)SePh] ( 2 ). A one‐pot reaction starting out from FcSnCl₃ gave [(FcSn)₉(OH)₆O₈Cl₅] ( 4 ), which represents the largest Fc‐decorated Sn/O cluster reported to date.     

Tin dithiocarbamates: applications and structures

The uses and potential utility of tin/organotin dithiocarbamate, ^?S₂CNR′₂, compounds are reviewed. Various derivatives exhibit exciting potential as anti‐cancer agents, anti‐microbial agents and insecticides, e.g. against mosquito larvae. Tin dithiocarbamates have also proven useful as precursors for tin sulfide nanoparticles. There is a wealth of structural data available for such compounds and with the exception of the diorganotin bis(dithiocarbamate) compounds, R₂Sn(S₂CNR′₂)₂, compounds for which different structural motifs are evident, there is a certain degree of homogeneity in the molecular structures for each class of compound unless there are additional coordination sites on the R and/or R′ groups. Owing to the strong coordination potential of the dithiocarbamate ligand for tin, supramolecular aggregates involving secondary Sn…S interactions are the exception rather than the norm. Copyright © 2008 John Wiley & Sons, Ltd.     

Mono-organotin(IV) compounds as esterification and transesterification catalysts

A series of monoorganotin(IV) compounds has been investigated as transesterification catalysts for the reaction of butyl propionate with methanol. The most active catalysts were found to be those which contain tin-halogen bonds, e.g. monobutyltin trichloride (BuSnCl₃), and the least effective were the coordinatively saturated monoorganotin derivatives. Certain of the mono(2-carboalkoxyethyl)tin compounds were found to undergo a facile autocatalysed transesterification reaction with alcohols. Coordination of the carbonyl group in the ester to the tin catalyst is an important factor influencing its activity. A study of the catalysis of the esterification of propionic acid by BuSnCl₃ is reported.     

SYNTHESIS AND CHARACTERISATION OF TIN(IV) AND ORGANOTIN(IV) COMPLEXES OF [N′-2-HYDROXYPHENYL-6-METHYLPYRIDINE-2-CARBALDIMINE. X-RAY CRYSTAL STRUCTURES OF n-BUTYLDICHLORO[N′-2-HYDROXYPHENYL-6-METHYLPYRIDINE-2-CARBALDIMINATO(1-)N,N′,O]TIN(IV) AND DIPHENYLCHLORO [N′-2-HYDROXYPHENYL-6-METHYL-PYRIDINE-2-CARBALDIMINATO(1-) N,N′,O]TIN(IV)

Abstract

The reactions of N′-2-hydroxyphenyl-6-methylpyridine-2-carbaldimine (LH) with tin(IV) chloride and organotin(IV) chlorides result in the formation of the corresponding tin(IV) and organotin(IV) complexes in which LH behaves as a uninegative tridentate ligand coordinating to the central tin atom via an N,N,O donor set. Crystal structure determinations of two of the compounds, n-butyldichloro[N′-2-hydroxyphenyl-6-methylpyridine-2-carbaldiminato(l-)N,N′,O]-tin(IV) (BuSnCl₂.L) and diphenylchloro[N′-2-hydroxyphenyl-6-methylpyridine-2-carbaldiminato(l-)N,N′,O]tin(IV) (Ph₂SnCl.L), have been performed and both structures feature distorted octahedral geometries about the tin centres. Systematic differences in the Sn-ligand separations are rationalised in terms of the reduced Lewis acidity of tin in Ph₂SnCl.L.     

Synthesis and characterization of tin(IV)/organotin(IV) complexes with 2-benzoylpyridine-N(4)-cyclohexylthiosemicarbazone [HBPCT]: X-ray crystal structure of [SnCl3(BPCT)]

Four new tin(IV)/organotin(IV) complexes, [SnCl₃(BPCT)] (2), [MeSnCl₂(BPCT)] (3), [Me₂SnCl(BPCT)] (4), and [Ph₂SnCl(BPCT)] (5), have been synthesized by the direct reaction of 2-benzoylpyridine-N(4)-cyclohexylthiosemicarbazone [HBPCT, (1)] and stannic chloride/organotin(IV) chloride(s) in absolute methanol under purified nitrogen. HBPCT and its tin(IV)/organotin(IV) complexes (2–5) were characterized by CHN analyses, molar conductivity, UV-Vis, FT-IR, and ¹H NMR spectral studies. In all the complexes, tin(IV) was coordinated via pyridine-N, azomethine-N, and thiolato-S from 1. The molecular structure of 2 has been determined by X-ray single-crystal diffraction analysis. Complex 2 is a monomer and the central tin(IV) is six-coordinate in a distorted octahedral geometry. The crystal system of 2 is monoclinic with space group P121/n1 and the unit cell dimensions are a?=?8.3564(3)?Å, b?=?23.1321(8)?Å, c?=?11.9984(4)?Å.     

Syntheses and characterization of pentacoordinate organo-tin(IV) complexes II

Nine substituted benzoyl hydrazonyl, three semicarbazonyl, and four thiosemicarbazonyl tridentate ligands were synthesized. They were used to coordinate with Bu₂SnCl₂ or (PhCH₂)₂SnCl₂ to form 18 novel tin complexes that contained pentacoordinate organotin(IV) in a heterobicyclic ring. All these complexes were characterized by MS, NMR, and IR spectroscopy elemental analyses. © 1995 John Wiley & Sons, Inc.