Triphenyltin Moiety Research Articles

Modified polymethyl methacrylate as a sustainable medium for capturing carbon dioxide

This study evaluates the potential of modified polymethyl methacrylate (PMMA) materials, which incorporate organotin moieties pendant on the polymeric chains, as media for carbon dioxide storage. The PMMA containing a triphenyltin moiety has the largest specific surface area (SBET=11.618 m2/g) in comparison to the polymers containing tributyl (5.287 m2/g) and trimethyl (4.881 m2/g) residues. The PMMA with the triphenyltin moiety proved to be the most efficient material in capturing carbon dioxide (34.8 cm3/cm, 6.8 wt%), which is attributed to its relatively high surface area and pore volume and diameter compared to the others.

Synthesis, characterization, X-ray structure and in vitro antifungal activity of triphenyltin complexes based on pyrazole dicarboxylic acid derivatives

A series of new ditriphenyltin(IV) dicarboxylate complexes of general formula (Ph3SnOOC-Pz)2R with Pz: pyrazole and R: alkyl or ether, have been synthesized from bipyrazoledicarboxylic acid and hydroxytripheyltin. These complexes, noted C1-C7, have been characterized by IR, 1H and 13C NMR spectroscopies. The molecular structures of C3: 1,3-Bis[(5-methyl-2-H-3-triphenyltincarboxylate pyrazol)]propane and C7: Bis[(2-methyl-2-H-3-triphenyltincarboxylate pyrazol)ethyl]oxide have been confirmed by single crystal X-ray diffraction. Both compounds crystallize in the monoclinic symmetry: C3 in P21 space group with a = 15.915(1) Å, b = 10.0791(8) Å, c = 13.823(1) Å, α = 90°, β = 100.459(3)°, γ = 90° and C7 in P21/n space group, with a = 15.0951(7) Å, b = 8.9847(3) Å, c = 34.244(1) Å, α = 90°, β = 101.421(2)°, γ = 90°. The two cristallographically independent Sn1 and Sn2 atoms are tetra coordinated within distorted tetrahedral environments, very similar in the two compounds. The antifungal activity of these organotin complexes and their corresponding bipyrazoledicarboxylic acid (ligands) has been evaluated against the pathogenic Fusarium oxysporum f. sp. albedinis. This activity greatly depends on the nature of ligands and on the dose used. The presence of triphenyltin moiety improves considerably the antifungal activity becoming close to that of the benomyl (fungicide).

Hyperfine Interactions and Metal Atom Dynamics in a Number of Stannyl Phosphide Compounds and the Detailed Crystal Structure of Triphenyltin Chloride Revisited

Temperature-dependent 119Sn Mossbauer effect (ME) spectroscopy has been used to elucidate the hyperfine parameters (isomer shift and quadrupole splitting) as well as the dynamics of the motion of tin in three triphenyltin phosphide complexes, namely P(SnPh3)3 (C54H45PSn3, 1), P7(SnPh3)3 (C54H45P7Sn3, 2), and [Na(benzo-15-crown-5)][P(SnPh3)2] (C50H50NaO5PSn2, 3), as well as in triphenyltin chloride (4). Although the isomer shifts are very similar for all four compounds, the quadrupole splitting is dependent upon their detailed structures. The metal atom vibrations are essentially isotropic with respect to the principal symmetry axis passing through the tin atom and the triphenyltin moiety. The crystal structure of triphenyltin chloride has been re-determined at four different temperatures, and the root-mean-square amplitudes-of-vibration of the metal atom have been evaluated from the crystallographic Ui,j values and compared with the corresponding data derived from the Mossbauer measurements. These metal atom dynamics have been compared with those of the stannyl phosphide complexes derived from ME data and related to their structural details. The sensitivity of the ME technique with respect to elucidating the metal atom dynamics is demonstrated in detail.

The influence of crystal packing effects upon the molecular structures of Ph3Sn(CH2)nSnPh3, n = 1 to 8, as determined by X-ray crystallography and DFT molecular orbital calculations. Supramolecular aggregation patterns sustained by C–H⋯π interactions

Crystallography shows that with the exception of the n = 1 and n = 6 derivatives, molecules of dinuclear Ph3Sn(CH2)nSnPh3, n = 1 to 8, display extended conformations where a pair of triphenyltin moieties are linked by methylene bridges of varying length. Discernable supramolecular aggregation patterns stabilised by C–H⋯π contacts lead to chains and ladders or even 2D arrays in most of the solid-state structures. In all but the n = 1 molecule, with inherent steric hindrance which precludes the adoption of molecular symmetry, symmetry is evident in all of the geometry optimised structures calculated using DFT methods; non-systematic variations in geometric parameters apparent in the experimental structures do not persist in the theoretical structures. The greatest disparity between the experimental and theoretical structures is found for the n = 6 compound, featuring a hexamethylene bridge. The linear conformation calculated in the gas-phase distorts to form a curved molecule to allow the more efficient crystal packing of spherical molecules, as for the spherical n = 1 molecule. In the remaining structures, the global crystal packing is based on the stacking of rod-like molecules.

Crystal Structure of Di-iso-butylammonium Thiolactatotriphenylstannate

The title compounds, [(iso-C4H9)2NH2][SnPh3(O2CCH(CH3)S)], crystallized in a monoclinic space group P21/n with the following cell parameters: a = 9.8537(2)A, b = 16.7775(3)A, c = 17.5845(3)A, β = 103.7740(10)°, V = 2823.48(9)A3, Z = 4 and Dx = 1.375 Mg m-3. The structure was refined to a final R value of 0.0222 for 5042 reflections [I > 2σ(I)]. The structure of the complex is ionic consisting of an anionic triphenyltin moiety and a cationic di-iso-butylammonium portion. In addition, a hydrogen bonding network between the cations and anions was observed.

Preparation of new organotin polymers via exchange reactions

PurposePreparation of new organotin polymers via a new synthetic route based on the exchange reactions of pentachlorophenyl acrylate or methacrylate with amino‐tri‐phenyltin benzoates or hydroxyl‐tri‐phenyltin benzoates.Design/methodology/approachThe pentachlorophenyl acrylate or methacrylate was prepared by polymerisation in solution with azobisisobutyrontrile as a free radical initiator. The polymers obtained were allowed to undergo exchange reactions with amino‐tri‐phenyltin benzoates or hydroxyl‐tri‐phenyltin benzoates. The structure of the polymers prepared was confirmed by IR spectroscopy. Films were prepared from purified organotin polymers solution on glass, PVC and tin plates. The release of tin compound from the films, when immersed in aqueous media, was assessed. The concentration of the released tin (ppm) was measured by atomic adsorption spectrophotometer.FindingsThe new synthetic route was effective, the organotin polymers prepared had good film properties and the release of tin compounds increased with the content of tin in the organotin polymers.Research limitations/implicationsThe alkaline resistance of the polymeric films prepared needs improvement.Practical implicationsThe polymers prepared provide a family of effective polymeric fungicide useful for a number of applications including water sterilisation.Originality/valueThe polymers prepared contained pendent triphenyltin moieties which slowly hydrolysed to give fungicidal and antifouling effects.

Communication: Synthesis of a Novel Triphenyltin(IV) Derivative of 2‐Mercaptonicotinic Acid with Potent Cytotoxicity in vitro

A novel triphenyltin(IV) derivative of 2-mercaptonicotinic acid (H2mna) of formula {[(C6H5)3Sn]2(mna).[(CH3)2CO]} (1) has been synthesized and characterized by elemental analysis and 1H, 13C-NMR, and FT-IR spectroscopic techniques. The crystal structure of complex (1) has been determined by single crystal X-ray diffraction analysis at 173(1) K. Compound (1) contains two triphenyltin moieties linked by a doubly de-protonated 2,mercaptonicotinic acid (H>2mna). It is an example of a pentacoordinated Ph3SnXY system with an axial-equatorial arrangement of the phenyl groups at Sn(1). Compound (1), exhibits potent, in vitro, cytotoxicity against sarcoma cancer cells (mesenchymal tissue) from the Wistar rat, polycyclic aromatic hydrocarbons (PAH, benzo[a]pyrene) carcinogenesis.

Bis[(N,N-3-oxapentamethylenethiocarbamoylthioacetato)triphenyltin] hydrate and bis(dicyclohexylammonium) bis(3-oxapentamethylenethiocarbamoylthioacetate)

In the two independent dinuclear molecules of bis-[(N, -3-oxapentamethylenethiocarbamoylthioacetato)triphenyltin] hydrate, [Sn 2 (C 6 H 5 ) 6 (C 7 H 10 NO 3 S 2 ) 2 (H 2 O)], the aqua(N,N-3-oxapentamethylenethiocarbamoylthio-acetato)triphenyltin moiety uses its carbonyl O atom to connect to the Sn atom of the (N,N-3-oxapentamethyl's enethiocarbamoylthioacetato)triphenyltin moiety, to furnish trans-C 3 SnO 2 trigonal bipyramidal geometries for the Sn atoms in the dinuclear compound. Hydrogen bonds link the coordinated water of one symmetry-independent molecule to the carbonyl and heterocyclic O atoms of the other independent molecule [O...O = 2.66(4) and 2.75(2), and 2.769(8) and 2.667(7) A, respectively] in a layer structure. The orthorhombic unit cell of bis(dicyclohexylammonium) bis(3-oxapentamethylenethiocarbamoylthioacetate), 2C 12 H 24 N + .-2C 7 H 10 NO 3 S 2 - , contains four centrosymmetric clusters of two cations and two anions. The C-O bonds in the carboxyl -CO 2 fragment of the anion are delocalized. The ammonium N atom is hydrogen bonded to two carboxyl O atoms belonging to different anions [N...O = 2.732(4) and 2.738 (4) A] to form an eight-membered O-C-O...N...O-C-O...N... ring.

Fungicidal Activity of Some Organotin Compounds againstCeratocystis ulmi

Three series of organotin compounds were screened in vitro against Ceratocystis ulmi, the causative agent of Dutch elm disease. The series that were most active against this deadly fungus were those that contained the triphenyltin moiety. In addition, the fungicidal activity of the triphenyltin compounds were found to be independent of the anionic group attached to the tin atom. However, there was a marked increase in the activity of the triphenyltins when a biologically active group which did not dissociate upon dissolution was incorporated into the overall molecule.

Triphenyltin(IV) isobutoxide isobutanol solvate

The structure consists of monomeric Ph 3 SnO i Bu.- i BuOH molecules, which are linked together by hydrogen bridges to give one-dimensional chains. Each molecule has a nearly trigonal-bipyramidal structure with a distorted trigonal-planar triphenyltin moiety and an isobutoxide group and an isobutanol molecule in axial positions. The correspondin tin-oxygen distances are 2.065 (5) and 2.550 (6) A, respectively

Tolerance of aggressive and non‐aggressive isolates of Ceratocystis ulmi to organotin fungicides

AbstractThe effect of triorganotin compounds, R3SnX, on the growth of three wild strains of Ceratocystis ulmi (C. ulmi) fungus, two aggressive and one non‐aggressive strains, was evaluated in shake culture. In all cases, the triphenyltins were the more effective organotins for the inhibition of C. ulmi in vitro. The anionic group, X, did not have a significant role in the inhibition, suggesting that the species involved in the inhibition is the triphenyltin moiety (Ph3Sn+) or the hydrated triphenyltin moiety (Ph3Sn(H2O)+2). It is further suggested that the triphenyltin species Ph3SnOH and Ph3SnOAc are the preferred compounds for the control of Dutch elm disease. The tolerance of aggressive isolates to fungitoxins appears to depend more on the nature of the fungicide than on the type of fungus.

Some exchange reactions involving phenyltin hydrides and organotin halides

Reaction of diphenyltin dihydride with diphenyltin dichloride or diphenyltin dibromide in a 1 : 1 mole ratio gives good conversion to diphenyltin chloride hydride and diphenyltin bromide hydride, respectively. Triphenyltin hydride with diphenyltin dichloride or diphenyltin dibromide in a 1 : 1 mole ratio gives fair conversion to the corresponding halide hydrides but less than in the case of diphenyltin dihydride. Diphenyltin dihydride reacts with dialkyltin dichloride in a 1 : 1 mole ratio to give a preponderance of organotin chloride hydride along with diphenyltin dihydride but no dialkyltin dihydride. However, triphenyltin hydride did not appear to react with dialkyltin dihidides in a 1 : 1 mole ratio to yield either the dialkyltin halide hydride or the dialkyltin dihydride. Reactions attempted between triphenyltin hydride and several trialkyltin chlorides confirm the tendency of the hydride hydrogen to become attached to the triphenyltin moiety rather than the trialkyltin or the dialkylchlorotin moieties.

Triphenyl Tin Compounds as Insect Reproduction Inhibitors1

Using the house fly, Musca domestica L., as an indicator, numerous triphenyl tin derivatives were found to act as reproduction inhibitors. The more active compounds such as Dowco2 186 (triphenyl tin hydroxide), Dowco 187 (allyl triphenyl tin), and Dowco 188 (bis (triphenyl tin) sulfide) have 3 phenyl groups in common, plus a fairly labile fourth group attached to tin. These compounds sterilize adult flies well below the lethal concentration. Females are sterilized at lower concentrations than males. Some derivatives produce easily reversible reproduction control; some do not. This property is somewhat dosage dependent in the house fly with all gradations ranging from nearly complete ovarian suppression to deposition of normal sized but sterile eggs. Triphenyl tins suppress or control reproduction in the German cockroach Blatella germanica (L.), and the confused flour beetle, Tribolium confusum Jacquelin du Val. The triphenyl tin moiety would appear to have promise for the reproduction control of insects and related species from several orders of arthropods.