The synthesis, Mössbauer and vibrational spectra of some triorganotin derivatives of phosphorus oxyacids

1976 ◽  
Vol 54 (14) ◽  
pp. 2184-2192 ◽  
Author(s):  
T. Chivers ◽  
J. H. G. Van Roode ◽  
J. N. Ruddick ◽  
J. R. Sams

Trimethyltin hypophosphite, Me3SnPO2H2, bis(trimethyltin) phosphite dihydrate, (Me3Sn)2PO3H.2H2O, and bis(triphenyltin) phosphite, (Ph3Sn)2PO3H, have been obtained from the organotin chloride and aqueous solutions of the sodium salt of the corresponding phosphorus oxy-acid. (Me3Sn)2PO3H.2H2O can be dehydrated under vacuum at 25 °C, but disproportionation occurs on heating. Tris(trimethyltin) orthophosphate, (Me3Sn)3PO4, was prepared from trimethyltin chloride and silver phosphate in methanol and gave an adduct formulated as [Formula: see text] after recrystallization from 1,4-dioxane. Vibrational spectra and Mössbauer data for Me3SnPO2H2 are consistent with a trigonal bipyramidal structure in which planar Me3Sn groups are bridged symmetrically by PO2H2 groups. The Mössbauer spectra of (Me3Sn)2PO3H, (Ph3Sn)2PO3H, and (Me3Sn)2PO3H.2H2O suggest that the two tin atoms are in similar (probably pentacoordinate) environments, implying at least one three coordinate oxygen per formula unit. For (Me3Sn)3PO4, the vibrational spectra, Mössbauer data, and physical properties are consistent with a weakly associated structure in which all three tin atoms are in similar environments. It is suggested that association is achieved via the phosphoryl (P=O) oxygen atom, which is weakly coordinated to three tin atoms leading to a distortion of the tetrahedral arrangement around tin towards trigonal bipyramidal.

1995 ◽  
Vol 73 (1) ◽  
pp. 95-99 ◽  
Author(s):  
Frank E. Smith ◽  
Rosemary C. Hynes ◽  
John Tierney ◽  
Ying Z. Zhang ◽  
George Eng

The title compound was synthesized as part of an effort to produce a more effective fungicide to combat Dutch Elm Disease (DED), which is caused by the fungus Ceratocystisulmi. A full X-ray structural analysis of the 1:1 adduct has been carried out and the results are reported along with the Mössbauer data for the compound. The crystals are monoclinic, space group P21/a with a = 19.240(3) Å, b = 9.1463(24) Å, c = 19.3512(24) Å, β = 118.874(8)°, V = 2982.0(10) Å3, z = 4, and Dcalc = 1.427 Mg m−3. The final discrepancy factors are RF = 0.056 and Rw = 0.058 for 1915 significant reflections. The QS and IS values in the Mössbauer spectrum of the complex are 3.08 mm s−1 and 1.28 mm s−1, respectively. The 2,3-diphenylthiazolidin-4-one behaves as a monodentate ligand and coordinates to the tin through the oxygen atom. The complex exhibits a trigonal bipyramidal configuration with the three phenyl groups in equatorial positions and the chloride and ligand oxygen occupying the apical sites. Keywords: triorganotin, fungicide, Dutch Elm Disease, thiazolidin-4-one.


1980 ◽  
Vol 58 (15) ◽  
pp. 1566-1576 ◽  
Author(s):  
Laurence K. Thompson ◽  
Richard G. Ball ◽  
James Trotter

A series of copper(II) complexes of the title ligand are reported which exhibit both five-coordinate trigonal bipyramidal and pseudo-octahedral stereochemistries. Mixed stereochemistry complexes [Cu(NTBT)X]2[CuX4] (X = Cl, Br), [Cu(NTBT)Br]2[Cu2Br6]•CH3CN, and the complexes [Formula: see text], [Formula: see text], contain trigonal bipyramidal cations while six-coordinate structures are implicated in the Systems [Cu(NTBT)Br2]•H2O and [Cu(NTBT)(H2O)2•MeOH•H2O. The molecular structure of [Formula: see text] has been determined by single crystal X-ray diffractometry. The crystal is monoclinic and belongs to the space group C2/c with Z = 8, a = 24.254(3), b = 14.107(2), c = 16.329(2) Å and β = 105.94(1)°. The complex adopts a distorted trigonal bipyramidal structure (no axial symmetry) with the ligand coordinating in a 'tripod' fashion as an N4 donor. The fifth ligand is a monodentate nitrate. The mean Cu—N distance is 2.07(3) Å and the Cu—O distance is 1.938(3) Å. A second nitrate oxygen atom is close to the copper centre (Cu—O distance 2.783(4) Å) and may represent a weakly bound sixth ligand. Both infrared and electronic spectral data support the presence of a sixth ligand.


2020 ◽  
Vol 4 (1) ◽  
pp. 17-23
Author(s):  
Muhammad Tariq ◽  
Ahmad Kaleem Qureshi ◽  
Muhammad Hamid ◽  
Naseem Abbas ◽  
Ajaz Hussain ◽  
...  

AbstractNew organotin (IV) complexes with NaL1 (sodium salt of 2-[[4-(3-methoxy-propoxy) 3-methylpyridin-2-yl]methylsulfinyl]benzimidazol-1-ide) and NaL2 (sodium salt of 3- aminomethyl-5-methylhexanoic acid) were synthesized by the reaction of diorganotin (IV) and triorganotin (IV) salt (Bu3SnCl, Ph3SnCl, Bu2SnCl2, Me2SnCl2) using the solvent (dry toluene) by constant stirring and refluxing. All the organotin (IV) complexes were characterized by different diagnostic techniques such as FT-IR (Infra-red) and UV-visible spectroscopy. The results exhibited that ligand NaL1 (sodium salt) is attached to tin metal by a nitrogen atom of benzimidazole ring and the oxygen atom of the sulfonyl group. While ligand NaL2 (sodium salt) coordinate with tin(IV) moiety through oxygen atom of the carboxylate group. The newly synthesized complexes 1 & 2 of ligand NaL1 (sodium salt) showed trigonal bipyramidal geometry while complexes 3 & 4 octahedral geometry around tin(IV) centre. The organotin(IV) complexes 5-7 of ligand NaL2 (sodium salt) have the tetrahedral geometry around tin(IV) centre. The synthesized complexes (1-7) were tested for antifungal and antibacterial microbial activities. All the complexes showed significant antibacterial and anti-fungal activities against tested bacterial and fungal strains.


1975 ◽  
Vol 9 (10) ◽  
pp. 616-618 ◽  
Author(s):  
A. F. Nikolaev ◽  
V. M. Bondarenko ◽  
O. F. Ginzburg ◽  
V. G. Rupyshev

2021 ◽  
Vol 77 (1) ◽  
pp. 67-74
Author(s):  
Jessica Donahue ◽  
Steven Hoehner ◽  
Ben Li

This article focuses on the problem of analytically determining the optimal placement of five points on the unit sphere {\bb S}^{2} so that the surface area of the convex hull of the points is maximized. It is shown that the optimal polyhedron has a trigonal bipyramidal structure with two vertices placed at the north and south poles and the other three vertices forming an equilateral triangle inscribed in the equator. This result confirms a conjecture of Akkiraju, who conducted a numerical search for the maximizer. As an application to crystallography, the surface area discrepancy is considered as a measure of distortion between an observed coordination polyhedron and an ideal one. The main result yields a formula for the surface area discrepancy of any coordination polyhedron with five vertices.


IUCrData ◽  
2017 ◽  
Vol 2 (10) ◽  
Author(s):  
Chunhua Fu ◽  
Rufen Zhang ◽  
Shaoliang Zhang

A new trimethyltin(IV) coordination polymer, [Sn(CH3)3(C7H8O2P)], has been prepared by treatment of methylphenylphosphinic acid and trimethyltin chloride with sodium ethoxide in methanol. In the solid state, the title compound adopts an infinite one-dimensional polymeric chain structure with each SnIVatom adopting a distorted trigonal–bipyramidal geometry.


1990 ◽  
Vol 55 (10) ◽  
pp. 2521-2536 ◽  
Author(s):  
Marcela Krečmerová ◽  
Hubert Hřebabecký ◽  
Antonín Holý

Reaction of sodium salt of 3-N,3'-O-bis(benzyloxymethyl)-2'-deoxyuridine (X) and 3-N,3'-O-bis(benzyloxymethyl)-2'-deoxythymidine (XI) with diethyl p-toluenesulfonyloxymethanephosphonate in dimethylformamide afforded diesters of the respective 5'-O-phosphonomethyl derivatives XII and XVII. Diethyl esters of 5'-O-phosphonomethyl-2'-deoxynucleosides XV and XIX, obtained after hydrogenolytic removal of the benzyloxymethyl groups, were converted into free 2'-deoxy-5'-O-phosphonomethyluridine (XVI) and a mixture of anomeric 1-(2-deoxy-5-O-phosphonomethyl-β-D-erythro-pentofuranosyl)thymines (XXIIIa, XXIIIb), respectively. Analogously, 2'-deoxy-5'-O-phosphonomethylcytidine (XXXIV) was prepared from 4-N-benzoyl-2'-deoxy-3'-O-(tetrahydro-2H-pyran-2-yl) cytidine (XXX) via diethyl ester of 2'-deoxy-5'-O-phosphonomethylcytidine (XXXIII). This compound reacted with bromotrimethylsilane to give compound XXXIV without anomerization and nucleoside bond cleavage. Condensation of the protected nucleosides X and XI with dibenzyl p-toluenesulfonyloxymethanephosphonate afforded dibenzyl esters of the corresponding 5'-O-phosphonomethyl derivatives XIII and XVIII. The free 5'-O-phosphonomethyl derivatives XVI and XXIIIa were obtained from XIII and XVIII by catalytic hydrogenation.


1995 ◽  
Vol 73 (11) ◽  
pp. 1948-1954 ◽  
Author(s):  
Pavol Hrdlovič ◽  
Lubica Horinová ◽  
Štefan Chmela

A multifunctional probe based on pyrene, the chloride of the 2,2,6,6-tetramethyl-4-hydroxy-piperidinium ester of 4-(1-pyrene)butyric acid, at a concentration of 5 × 10−5 mol dm−3 exhibits excimer-like green emission with the maximum at 480 nm in the presence of sodium dodecylsulfate below its critical micelle concentration. A similar effect has been observed for this probe in the presence of the sodium salt of polyacrylic acid in the same concentration range. 1-Pyrenemethylammonium chloride exhibits a broad green excimer-like emission for sodium dodecylsulfate but not for the sodium salt of polyacrylic acid. The quenching constants of the monomeric and excimer-like emissions were determined for acrylamide, 1-oxo-2,2,6,6-tetramethyl-4-hydroxypiperidine, potassium iodide, and copper(II) sulfate, representing neutral, ionic, and free-radical types of quenchers. The rate constants of quenching for N-oxyl radicals indicate that the monomeric emission from both water-soluble probes is diffusion controlled. For other types of quenchers the rate constant of bimolecular quenching is lower. The quenching of the excimer-like emission of an aggregate of the chloride of the 2,2,6,6-tetramethyl-4-hydroxypiperidinium ester of 4-(1-pyrene)butyric acid is less efficient than in the case of 1-pyrenemethylammonium chloride, which indicates a more packed structure of the former aggregate. Keywords: pyrene, ionic derivative, emission, micelle, aggregation, quenching.


1996 ◽  
Vol 51 (11) ◽  
pp. 1655-1662 ◽  
Author(s):  
Gabriele Wagner ◽  
Christian Heiß ◽  
Uwe Verfiirth ◽  
Rudolf Herrmann

Derivatives of 3-oxo-camphorsulfonimide (1) with two phenylethynyl groups in the endo positions at the carbons C-2 and C-3 were prepared, and their reactivity towards halogenes and titanium chloride was studied. In every case, the two ethynyl groups led to the annulation of a five-membered ring to the bicyclo[2 .2 .1] system in an orientation which depends on the bulkiness of the additional substituent in position 3. NMR studies show that cationic species like 6 and 8 are the first detectable intermediates. They not only contain the fused five-membered ring but also a bond between its exocyclic methylene carbon and an oxygen atom of the sulfonyl group, thus transferring the positive charge mainly to sulfur. Semiempirical calculations (PM3) suggest two intermediates in the formation of such cations.


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