Tin and tin compounds

prepared by Syracuse Research Corporation under contract no. 205-1999-00024 ; prepared for U.S. Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry."August 2005."Chemical manager(s)/author(s): Carolyn Harper, ATSDR, Division of Toxicology, Atlanta, GA; Fernando Llados, Gary Diamond, Lara L. Chappell,.Syracuse Research Corporation, North Syracuse, NY --P. ix."A toxicological profile for tin and tin compounds, draft for public comment was released in September 2003. This edition supersedes any previously released draft or final profile"--P. iii."This toxicological profile is prepared in accordance with guidelines developed by the Agency for Toxic Substances and Disease Registry (ATSDR) and the Environmental Protection Agency (EPA). The original guidelines were published in the Federal Register on April 17, 1987"--P. v.Also available via the World Wide Web.Includes bibliographical references (p. 309-369) and index

Novel six-coordinate Aryl- and Alkyltin complexes

Organo-tin compounds have wide applications as pesticides and as intermediates for organic synthesis.¹ They are invariably Sn(IV) derivatives and are generally four-coordinate.² The mixed organo/chioro compounds of the type RnSnCI4-n do however have the ability to expand their coordination numbers to five or six. This depends critically on the substituents - with four organic groups, R₄Sn, there is no tendency at all to coordinate extra ligands, while at the other extreme SnCl₄ readily forms six-coordinate [SnC1₄L₂] complexes since the electronegative halo groups increase the Lewis acidity of the tin centre

Tin compounds in food-their distribution and determination

The aim of this work was optimization of the methods of trace-and ultratrace analysis, such as ICP-OES, ETA-AAS for charting the resources of individual forms of tin in foodstuffs. Increase of the sensitivity of the method of ICP-OES was achieved using the techniques of generation of hydrides, which was also optimized. Based on the information available on the occurrence of the different forms of tin, it appears that many of these organometallic compounds are contained in marine animals; attention has mainly focused on organisms such as marine fish, crustaceans, molluscs and algae. Tin compounds of predominantly inorganic origin can be found in foods and beverages which are packed in cans with a protective tin coating, too. The above mentioned methods have been applied to the analysis of selected beverages with low content of tin such as Coca Cola, Sprite, Fanta, Gambrinus 10°, PowerKing, and milk in the cans. Furthermore samples of animal origin as Sardines in oil, and Hunter's salami were examined, too. Prior to the determination of tin, samples need to be appropriately modified or analysed. Decomposition of the samples was done in the microwave system. Low pressure ion exchange chromatography with on-line detection of ICP-OES was used for separation of inorganic tin compounds. Separation of organically bound tin compounds was performed by HPLC on a column of ACE C-18, 3 µm, 15 cm x 1.0 mm with off-line detection by ETA-AAS. All of the above forms of tin compounds can be separated with this column. Due to the improvement in the detection of organically bounded tin, HPLC with identical ACE C-18 column coupled online for example with ICP-MS or spectrofluorimetry could be recommended. © 2019 Muhammad Arba et al

A study of some cyclohexyl tin compounds

Although a large number of organotin compounds have been prepared (Dr. Garzuly lists over one hundred and fifty), comparatively little is known about them. It was the purpose of this investigation to study some of the cyclohexyl tin compounds with a view toward finding out more about their preparation and properties, and to prepare some that had not been prepared before. Unfortunately time and circumstances prevented the latter

Solid-state N.M.R. studies of platinum and tin compounds

High-resolution solid-state N.M.R. studies of dilute spins are now possible using cross-polarisation and MAS techniques. A systematic evaluation has been undertaken to determine their applicability to spin-½ metal nuclei, in particular (^195)Pt and (^119)Sn. In addition, an extensive (^13)C and (^31)p solid-state N.M.R. study has been carried out on a selection of Pt(II) complexes, supplying information on isotropic (scalar) coupling constants and shielding anisotropy. The majority of (^119)Sn and (^195)Pt spectra exhibit a multitude of spinning sidebands due to the large shielding anisotropy present. The tin systems under study have been of type R(_3)SnX (where R = Alkyl, phenyl and X = F, OH, CI); some are shown to be polymeric in the solid-state with penta-coordinate tin present. Where possible, correlations with X-ray crystallographic data and solution-state N.M.R. studies are giving. The interactions present in Pt(IV) compounds containing directly bonded quadrupolar nuclei have been studied and imply motional activity present in the solid- state. A more comprehensive study of these effects is given for two tin systems (Ph(_3)SnCl and (NH(_4))(_2)SnCl(_6)), whereby observed splittings can be accounted for by a combination of (^119)Sn-Cl dipolar and scalar coupling. The interplay of tensor properties between spin-½ nuclei, namely (1) dipolar coupling, (11) indirect (scalar) coupling and (111) shielding anisotropy is explored in solid-state (^195)pt-(^31)p and (^119)sn-(^19)f systems. The theory for such tensorial interplay is given for an AX(_2) system

NMR studies of some solid silver and tin compounds

A solid-state NMR study of a range of tin- and silver-containing compounds has been carried out in order to obtain information on the chemical shifts, coupling constants and relaxation times. The results are discussed in relation to the crystal structures, where known, and some crystallographic information obtained in cases with no previously-known structures. For tin-containing compounds, solid-state (^119)Sn and (^31)P NMR comprise the majority of this work. Nevertheless, (^13)C NMR studies have been also carried out to assist the structure determination. Six Sn(II) compounds have been examined, including three which also contain phosphorus. Spinning sideband analysis has been achieved for (^119)Sn (in some cases (^31)P), giving information on the shielding tensors. Satellite peaks observed on the (^119)Sn NMR spectra of SnHPO(_3) and SnHP0(_4) reveal that the spectra contain information about indirect Sn(_2)Sn coupling. Since surprisingly large values of 2600 ±200 Hz and 4150 ± 200 Hz are found for SnHPO(_3)and SnHPO(_4), respectively, the calculated relative intensities of the satellites and the results of a single Hahn echo experiment have been discussed in detail. The relatively isolated ((^1)H,(^31)P) spin pair in solid SnHPO(_3) have been extensively investigated in this work, though the systems are rather complicated. The (^1)H and (^31)P spectra display an intensity distribution of the spinning sidebands, which is the characteristic of an interplay of shielding, dipolar and indirect coupling tensors dominated, by the strong dipolar interactions. A single Hahn echo experiment was employed to reveal indirect spin-spin coupling ((^1)JPH). Strong oscillatory polarization transfer by dipolar interaction occurs during short contact times on moderately fast magic-angle spinning and the P,H distances were extracted (including for SnHPO(_4)).Rather complicated (^1)H NMR spectra under (^31)P continuous-wave decoupling arises from a second-order recoupling of the heteronuclear dipolar-coupling tensor and the shielding tensor of ^'P, leading to line-splittings and broadenings in the {(^31)P}(^1)H spectra. Additionally, measurement of (^1)H and (^31)P relaxation times has been undertaken, producing results which were expected to follow the behaviour characteristic of an isolated two-spin system, but anomalies were observed. Various nuclei, such as (^13)C, (^15)N, (^31)P and (^109)Ag, in silver-containing compounds have been studied, and provide information on indirect spin-spin interactions, (^1)J((^109)Ag (^14)N) and (^1)J((^109)Ag(^15)N). The (^109)Ag NMR spectra for [Ag(NH(_3)(_2))(_2)X where X = SO(_4), SeO(_4), NO(_3)show spinning sideband manifolds, which are typical for systems with moderately large shielding anisotropy. Other silver compounds namely [Ag(R)(_2)]NO(_3) where R = pyridine, collidine, 2-picoline, quinoline and AgY where Y = HPO(_4) and PO(_4), have been investigated to give as much complementary information about the chemical shifts as possible

Free-radical chain reactions of organic mercury and tin compounds

Alkylmercury halides (RHgX, R = n-butyl, n-hexyl, (DELTA)(\u273)-butenyl, (DELTA)(\u275)-hexenyl, isopropyl, cyclohexyl, cyclopentylcarbinyl and 7-norbornyl) rapidly react with PhYYPh (Y = S, Se and Te), p-MeC(,6)H(,4)SO(,2)SePh, PhSO(,2)Cl, PhSH and BrCCl(,3) under sunlamp irradiation to give RYPh, RCl, RH and RBr, respectively. The reaction is completely inhibited by di-tert-butyl nitroxide, does not occur in the dark and yields a mixture of cyclopentylcarbinyl and (DELTA)(\u275)-hexenyl products from the (DELTA)(\u275)-hexenylmercurial. The reaction is believed to proceed via a radical chain mechanism involving R(.) and Hg(III) intermediates. The alkyl radical (R(.)) undergoes S(,H)(\u272) or atom transfer reactions with the substrate and the resulting radical (PhY(.), PhSO(,2)(.) or (.)CCl(,3)) reacts with RHgX to form the Hg(III) intermediate which then eliminates R(.). A similar mechanism is proposed for the reaction of dialkylmercurials (R(,2)Hg, R = n-butyl, isobutyl and (DELTA)(\u275)-hexenyl) with PhSSPh and PhSeSePh. However, benzylmercurials (PhCH(,2)HgQ, Q = Cl and PhCH(,2)) react with phenyl dichalcogenide differently from other alkylmercurials, in that bibenzyl is formed in a chain reaction. Bibenzyl is also the product of the photostimulated chain decomposition of PhCh(,2)HgQ (Q = PhCH(,2) and PhS). Evidence is presented that the reaction of benzylmercurials proceeds by a free radical chain mechanism involving S(,H)(\u272) attack of the benzyl radical at the benzyl mercury bond;Tri-n-butyl-1-alkenyltin compounds containing a (beta)-phenyl substituent, PhCH=CHSnBu(,3) and Ph(,2)C=CHSnBu(,3), undergo a photostimulated reaction with 2(DEGREES)- or 3(DEGREES)-alkylmercurials to give PhCH=CHR and Ph(,2)C=CHR, Bu(,3)SnCl and Hg(0). The reaction was established to proceed via a radical chain process involving (alpha)-addition of the alkyl radical followed by (beta)-elimination of Bu(,3)Sn(.) and electron transfer from the tin-centered radical to the alkylmercurials. The reaction has been successfully extended to other (beta)-substituted styrenes, PhCH=CHQ (Q = I, PhSO(,2), HgCl and PhS) where Q(.) can be reacted with RHgX to generate R(.). In addition, PhCH=CHSnBu(,3) reacts with CCl(,3)Z (Z = Cl, Br and SO(,2)Cl) under UV irradiation to give exclusively PhCH=CHCCl(,3). Similarly, 1-alkenyltin derivatives with or without a (beta)-phenyl substituent, react with sulfur-centered radicals (PhS(.), PhCH(,2)S(.), PhSO(,2)S(.) and p-MePhSO(,2)(.)) derived from the reaction of Bu(,3)Sn(.) with PhSSPh, PhCH(,2)SSCH(,2)Ph, PhSO(,2)Cl or p-MeC(,6)H(,4)SO(,2)SePh to give the corresponding sulfides and sulfones in excellent yields