Triorganotin Halides Research Articles

Heptacoordinate Structures of Organotin Halides with Three Phosphine Donors: Halogen‐Substituent Effect on Geometry

Structural studies were performed on heptacoordinate compounds of triorganotin halides {(o‐Ph2P)C6H4}3SnX [X = F (1), Cl (3), Br (4), I (5)] with three phosphine donors. The fluorostannane (1) has an unusual heptacoordinate geometry, in which the three phosphine donors interact with the Sn center around the opposite coordination site of the Sn–F bond (a form). In contrast, the chloro (3) and bromo (4) analogues have highly distorted pentagonal‐bipyramidal geometries (b form), while the iodo analogue (5) has a tricapped tetrahedral geometry (c form). Although both b and c forms have two phosphine donors coordinating to the Sn center around the opposite site of the Cipso atoms and one phosphine donor coordinating to the Sn atom trans to the halogen atom, the geometry around the Sn center is much more distorted from tetrahedral geometry in b form than in c form. Density functional theory (DFT) calculations indicate that the presence of the halogen atom on the Sn center facilitates access from the opposite side of the halogen due to the strong electrostatic and intramolecular donor–acceptor transfer interactions. The difference in electronegativity of the halogen atoms also appear to contribute to structural modification by altering the halogen substituent, because a strongly electronegative halogen facilitates the formation of a structure that is highly distorted from the tetrahedral geometry (Bent's rule).

A Review of Organotin Compounds: Chemistry and Applications

The field of organotin chemistry has a long history that started since 1849, when Frankland isolated a specimen of diethyltin diiodide [1]. In 1852, Lowich reported on the reaction of alkyl halides with a tin-sodium alloy giving alkyltin compounds [2]. This last publication is usually considered to represent the beginning of organotin chemistry. By 1935, about hundreds of publications concerning organotin chemistry had appeared in the literature. At that time, important names had played a role in the development of organotin chemistry were Krause in Germany, Kraus in the United States, and Kozeshkov in Russia. The discovery of organotin compounds industrial applications as polyvinyl chloride (PVC) stabilizers, as agrochemicals, biocides, and wood preservatives produced a revival of organotin chemistry. Particularly van der Kerk and his co-workers in Netherlands played a major role in this development [3,4]. In early of 1960s it was found that the tin atom in organ tin compounds is capable of extending its coordination number beyond four. Based on colligative studies, the trimethyltin chloride pyridine adduct, Figure 1, was the first documented fivecoordinate triorganotin halide complex that was proven by X-ray crystal structure [5]. Though divalent tin compounds had known for a long time, bis (cyclopentadienyl) tin (II) was the first example of a divalent organotin compound that was reported in 1956 [6].

Organotin(IV) derivatives of o-isobutyl carbonodithioate: Synthesis, spectroscopic characterization, X-ray structure, HOMO/LUMO and in vitro biological activities

A series of organotin(IV) complexes have been synthesized by reacting potassium o-isobutyl carbonodithioate with di- and triorganotin halides in methanol under stirring conditions. The newly synthesized complexes have been characterized by elemental analysis, FT-IR, NMR (1H and 13C) and X-ray crystallography. The FT-IR results show that the ligand acts as bidentate in complexes 1–3 and monodentate in complexes 4 and 5, which were also confirmed by theoretical calculations. The NMR data reveal four and six coordinated geometries in solution. A HOMO–LUMO study shows that all the complexes are stable. Biological screenings demonstrate that, with a few exceptions, all the complexes show significant activity against various bacterial and fungal strains. The synthesized complexes were also found to be effective antioxidants of the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH). All the complexes have been assayed for antileishmanial activity in vitro and found some promising results. The UV–Vis studies confirmed that the ligand and its complexes bind to DNA via intercalative interactions, resulting in hypochromism and minor red shifts.

Design, structural and spectroscopic elucidation, and the in vitro biological activities of new triorganotin dithiocarbamates – Part II

The two novel dithiocarbamate salts, [Na{S2CNR(R1)}] (i), [Na{S2CNR(R2)}] (ii), R=methyl, R1=CH2CH(OMe)2, R2=2-methyl-1,3-dioxolane, previously synthesized by us, have been used in chemical reactions with triorganotin halides. Hence, five new complexes: [SnPh3{S2CNR(R1)}] (1), [SnCy3{S2CNR(R1)}] (2), [SnMe3{S2CNR(R2)}] (3), [SnPh3{S2CNR(R2)}] (4) and [SnCy3{S2CNR(R2)}] (5), [R=methyl, R1=CH2CH(OMe)2, and R2=2-methyl-1,3-dioxolane], have been isolated. All compounds were authenticated in terms of infrared, 1H and 13C NMR, and the complexes were also characterized using 119Sn NMR, 119Sn Mössbauer and X-ray crystallography, in the case of complexes (1), (4) and (5). The biological activity of all derivatives has been screened in terms of IC90 (μmolL−1) and IC50 (μmolL−1) against Aspergillus flavus, Aspergillus niger, Aspergillus parasiticus and Penicillium citrinum, and the results correlated well with a performed study of structure–activity relationship (SAR). Complexes (1) and (4) displayed nanomolar inhibition concentration in terms of IC50.

Polymer‐Supported Organotin Reagents for Regioselective Halogenation of Aromatic Amines.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Polymer-Supported Organotin Reagents for Regioselective Halogenation of Aromatic Amines

[reaction: see text] Polymer-supported triorganotin halides were used in the halogenation reaction of aromatic amines. Treatment of aromatic amines with n-butyllithium and polymer-supported organotin halides gave the corresponding polymer-bound N-triorganostannylamines, which by treatment with bromine or iodine monochloride gave the para-halogenated aromatic amines with high yields and high selectivities. The polymer-supported organotin halides reagents regenerated during the course of the halogenation reaction can be reused without loss of efficiency. The presence of tin residues in halogenated aromatic amines was also investigated and evaluated at under 20 ppm after three runs.

Coordination behaviour of the 2‐(N,N‐dimethylaminomethyl)phenyl ligand towards the di‐t‐butylchlorotin(IV) moiety

Abstract{2‐(N,N‐Dimethylaminomethyl)phenyl}(di‐t‐butyl)tin(IV)chloride, {2‐[(CH3)2NCH2]C6H4}Sn(t‐Bu)2 Cl, has been prepared and characterized using NMR and crystallography. This is the first example of a triorganotin(IV) halide containing the 2‐[(CH3)2NCH2]C6H4—group as a C,N‐chelating ligand with a weak intramolecular Sn—N interaction because of the steric hindrance of t‐butyl groups. The interatomic Sn—N distance is elongated to 2.904(14) Å and the central tin atom is distorted trigonal bipyramidal. Copyright © 2004 John Wiley & Sons, Ltd.

Short communication: Stille coupling reactions of functionalized triorganotin halides

AbstractConvenient conditions for the Stille coupling of halide‐bearing triorganotin compounds, which do not normally react under typical Stille reaction conditions, are presented. The coupling of vinylstannanes with allyl bromide using palladium(II) catalysis is accomplished under fluoride assistance to give the substituted 2,5‐hexadien‐1‐ols in Z‐configuration. Copyright © 2004 John Wiley & Sons, Ltd.

Simple Synthesis of Tetrabutylammonium and Potassium Salts of Difluorotriorganostannate and Silicate Anions

The title salts are readily prepared via stirring of triorganotin halides or triorganosilyl fluorides with tetrabutylammonium hydrogen sulfate and potassium, fluoride or sole potassium fluoride.

Cocatalysis by tetravalent tin compounds in phase-transfer catalyzed fluorination of alkyl halides and sulfonates

Phase-transfer catalyzed fluorination of alkyl halides or sulfonates is co-catalyzed efficiently by triorganotin halides. The cocatalytic action is due to continuous formation of lipophilic hypervalent triorganodifluorostannate anions, which act as fluorinating agents in the organic phase.

Synthesis and Reactivity of Organotin Compounds Containing the C,P-Chelating o-Carboranylphosphino Ligand [o-C2B10H10PPh2-C,P](CabC,P). X-ray Structures of (CabC,CH2P)SnMe2Br, [(CabC,P)SnMe2]2Pd, and [(CabC,P)SnMe2]Pd(PEt3)Cl

The triorganotin halides (CabC,P)SnMe2X (2a, X = Cl; 2b, X = Br) and a tetraorganotin compound (CabC,P)SnMe3 (7), containing the o-carboranylphosphino ligand (CabC,P), have been prepared by the reaction of LiCabC,P (1) with Me2SnX2 and Me3SnCl, respectively. 1H, 13C, 31P, and 119Sn NMR spectroscopy indicate that the tin centers in 2a and 2b are pentacoordinate as a result of intramolecular Sn−P coordination, whereas the tin center in 7 is tetracoordinate. The substitution reactions of 2a using NaI, NaN3, NaCpFe(CO)2, and NaB(CN)H3 afforded the substituted products (CabC,P)SnMe2X (3, X = I; 4, X = N3; 5, X = CpFe(CO)2; 6, X = H). The Wurtz-type coupling reaction of 2a with sodium afforded the distannane. The reaction of the distannane 10 with Pd2(dba)3·CHCl3 afforded the bis(stannyl)palladium complex 11. When compounds 2a and 2b were employed in the reaction with Pd2(dba)3, the halo-bridged metal complexes 12a and 12b were isolated. The crystal structures of 9b, 11, and 13 were determined by X-ray structur...

Chiral organotin hydrides containing intramolecular coordinating substituents

A series of chiral non-racemic triorganotin halides and triorganotin hydrides containing one or two (1 R,2 S,5 R)-menthyl (Men) substituents as well as the 8-dimethylaminonaphthyl (L) or 2-[(1 S)-1-dimethylaminoethyl]phenyl (L*) substituents has been synthesised and characterised. Each of the compounds MenPhLSnBr ( 1) and MenPhLSnH ( 2) has a stereogenic tin centre and the compounds were isolated in diastereomeric ratios of 60:40 and 66:33, respectively. Compounds MenPhL*SnCl ( 3) and MenPhL*SnH ( 4) were synthesised with diastereomeric ratios of 73:27 and 64:36, respectively. Single crystal X-ray analysis of MenPhL*SnCl ( 3), Men 2L*SnCl ( 8), and MenPh 2LSn ( 10) reveals that each structure has a tendency towards penta-coordination at the tin centre as a result of intramolecular N→Sn interactions. AM1 calculations successfully predict the molecular geometries observed in the solid state as well as the diastereomeric ratios observed in solution.

Synthesis and Reactivity of Intramolecularly Stabilized Organotin Compounds Containing the C,N-Chelating o-Carboranylamino Ligand [o-C2B10H10(CH2NMe2)-C,N]- (CabC,N). X-ray Structures of (CabC,N)SnR2X (R = Me, X = Cl; R = Ph, X = Cl), (CabC,N)2Hg, and [(CabC,N)SnMe2]2

A variety of organotin complexes, containing the o-carboranylamino ligand (CabC,N), has been prepared by the reaction of LiCabC,N (1) with organotin halides or tin tetrachloride. In this way, the tetraorganotin compound (CabC,N)SnMe3 (2), triorganotin halide (CabC,N)SnR2X (3: R = Me, X = Cl, 3a; R = Ph, X = Cl, 3b; R = Me, X = Br, 3c), diorganotin dichloride (CabC,N)SnPhCl2 (4), and monoorganotin trichloride (CabC,N)SnCl3 (5) have been synthesized and characterized. 1H and 119Sn NMR spectroscopy indicates that the tin center in the tetraorganotin compound 2 is tetracoordinate, whereas this center in mono-, di-, and triorganotin compounds 3−5 is pentacoordinate as a result of intramolecular Sn−N coordination. Complexes 3a,c were also formed by redistribution of (CabC,N)SnMe3 (2) with the corresponding Me2SnX2 (X = Cl, Br). The molecular structures of 3a,b were determined by X-ray analysis. As a result of the Sn−N interaction, the tin atoms in 3a,b exhibit distorted-trigonal-bipyramidal configurations with ...

Synthesis of chiral organotin hydrides containing menthyl and oxazoline substituents†

A series of chiral non-racemic triorganotin halides and triorganotin hydrides containing one or two (1R,2S,5R)-menthyl (Men) substituents as well as 2-(4,4-dimethyl-2-oxazolinyl)-5-(methyl)phenyl (L) or chiral 2-(4-isopropyl-2-oxazolinyl)-5-(methyl)phenyl ligand (L*) have been synthesized and characterised. Each of SnCl(Men)PhL and SnH(Men)PhL has a stereogenic tin centre and were isolated in diastereomeric ratios of 70∶30 and 50∶50, respectively; SnCl(Men)PhL* and SnH(Men)PhL* were synthesized in diastereomeric ratios of 50∶50 and 66∶34, respectively. Single crystal X-ray analysis of SnCl(Men)2L and SnCl(Men)PhL reveals a tendency towards five co-ordination at the tin centre as a result of N→Sn interactions. AM1 calculations provide good qualitative predictability of the molecular geometries observed in the solid state as well as the diastereomeric ratios in solution.

Transition-metal Schiff-base complexes as ligands in tin chemistry. Part 7. Reactions of organotin(IV) Lewis acids with [M(L)] 2 [M=Ni, Cu and Zn; H 2L= N,N′-bis(3-methoxysalicylidene)benzene-1,3-diamine and its -1,4-diamine analog

Dinuclear complexes [M(3MeO-sal- m-phen)(H 2O)] 2 [M=Cu, Ni and Zn; 3MeO–H 2sal- m-phen= N,N′-bis(3-methoxysalicylidene)benzene-1,3-diamine] and [M(3MeO-sal- p-phen)(H 2O)] 2 [M=Cu, Ni and Zn; 3MeO–H 2sal- p-phen= N,N′-bis(3-methoxysalicylidene)benzene-1,4-diamine] were synthesised and reacted with diorganotin(IV) dihalides, dinitrates and dithiocyanates. Only in the case of those reactions involving [M(3MeO-sal- m-phen)(H 2O)] 2 with M=Ni or Zn were adducts obtained as the sole products of reaction; the adducts were all tetranuclear complexes. The tetranuclear adduct {(SnBu n 2).[Ni(3MeO-sal- m-phen)(NCS) 2]} 2· 6MeCN results from salicylaldimine ligands, related by a 2-fold axis, adopting bridging roles by co-ordinating to each of the symmetry related nickel atoms through phenolic oxygen and imine nitrogen atoms, while their phenolic and methoxy oxygen atoms form donor bonds to the tin atoms of symmetry related dibutyltin cations. The salicylaldimine ligands, related by inversion, adopt the same bridging role towards the nickel atoms in the adduct {[SnBz 2(NO 3)]·[Ni(3MeO-sal- m-phen)(NO 3)]} 2.6MeCN (Bz=benzyl), but as a result of the bidentate role of the nitrate co-ordinated to nickel, the arrangement of the phenolic and methoxy oxygens is such that each tin is co-ordinated quite strongly by a bidentate nitrate, a methoxy and two phenolic oxygen atoms while a second methoxy oxygen provides a weak Sn–O interaction, thus resulting in pseudo eight co-ordinate tin. 119Sn Mössbauer parameters indicate that all of the adducts of di- and triorganotin halides are organotin aqua adducts with the donor water engaged in hydrogen bonding with Schiff-base oxygen atoms.

Sulphur(IV) compounds as ligands: XX. Adduct formation and ring opening of thiirane-1-oxide with organotin halides. Crystal structure of [(4-FC 6H 4) 2SnCl 2(C 2H 4SO) 2

The organotin halides R n SnX 4- n (R  Ph, 4-MeC 6H 4, 4-FC 6H 4; X  Cl, Br; n = 0, 1, 2, 3) and Me 2SnCl 2 form adducts with thiirane-1-oxide. In general, for n = 0, 1, 2 these have a 1: 2 stoichiometry and are octahedral, as shown by a single-crystal structural study of [(4-FC 6H 4) 2SnCl 2(C 2H 4SO) 2] ( 4c). In 4c the aryl groups are trans to each other and the chloride and sulphoxide ligands mutually cis. The SO bond is 0.04 Å longer than that in uncoordinated thiirane-1-oxide, whereas the bonds within the three-membered ring are shortened by a similar amount. Depending on the reaction conditions, 1:1 adducts [R 2SnX 2(C 2H 4SO)] (R = 4-MeC 6H 4, X  Cl, Br; R  Me, tBu, X  Cl) can also be isolated, while triorganotin halides form only 1:1 complexes. Analogous dimethylsulphoxide (DMSO) adducts have been synthesized for comparison. On the basis of vibrational spectroscopic data it can be concluded that thiirane-1-oxide is a weaker base than DMSO. This is supported by an NMR study of the formation of the 1:1 adduct between Me 2SnCl 2 and thiirane-1-oxide ( 9), which gave the following thermodynamic data: K eq = 8.6 M −1, Δ H R = −20.4 kJ mol −1, Δ S R = −50 J mol −1 K −1. Decomposition of the thiirane-1-oxide adducts at room temperature gives the thiosulphinic acid esters XC 2H 4S(O)SC 2H 4X (X  Cl: 18a, Br: 18b) in high yields.

Organometallic complexes with biological molecules II. Synthesis, solid‐state characterization and in vivo Cytotoxicity of Diorganotin(IV)chloro and Triorganotin(IV)chloro derivatives of Penicillin G

AbstractSeveral new diorganotin(IV)chloro and triorganotin(IV)chloro penicillin G derivatives have been prepared. The isolated compounds showed 1:1 stoichiometry, with formulae R2SnClpenG and R3SnClpenGNa, respectively (penG− = penicillin G− = 4‐ thia ‐ 1 ‐ azabicyclo[3.2.0]heptane‐2‐carboxylate, 3,3‐dimethyl‐7‐oxo‐6‐(2‐phenylacet‐amido) anion; R = Me, Bu, Ph). The coordination environment around the the tin(IV) atom, in all of the complexes, was trigonal bipyramidal. Penicillin G behaved as a monoanionic, bismonodentate ligand in R2SnClpenG through the β‐lactamic carbonyl and unidentate ester‐type carboxylate anion, and as unidentate through the β‐lactamic carbonyl in R3SnClpenGNa, as inferred on the basis of IR spectra.The rationalization of the Mössbauer parameter nuclear quadrupole splitting, ΔE (mm s−1), according to the point‐charge model formalism, supported such an hypothesis.The partial atomic charges on tin atoms, QSn, calculated for all the diorganotin(IV)chloropenG and triorganotin(IV)chloropenGNa compounds by the CHELEQ program, correlated well with the experimental 119Sn Mössbauer parameter isomer shift, δ (mm s−1). The δ/QSn data for diorganotin(IV)chloropenG and for triorganotin(IV)‐chloropenGNa dervatives have been correlated with the δ/QSn values of triorganotin(IV) halide, cyanide, thiocyanate and cyanate compounds, whose trigonal bipyramidal polymeric structure has been well established.Finally, the biological activity of diorganotin(IV)chloropenG and triorganotin(IV)chloropenGNa derivatives has been tested using Ciona intestinalis fertilized eggs at different stages of development.

Evidence for hexacoordinate tin centers in triorganotin halides containing two 8-(dimethylamino)-1-naphthyl ligands

A series of novel triorganotin halides, SnX[ 1-CloH6NMez-8]zR, containing two potentially intramolecular-coordinating 8-(dimethylamino)-l-naphthyl groups has been synthesized and characterized. The compounds were prepared via oxidative addition of an alkyl halide RX (R = Me, X = I; R = Et, X = I; R = benzyl, X = Br) to bis[&(dimethylamino)-1-naphthylltin(I1). From one of these compounds (R = Me, X = I) the molecular structure in the solid state has been determined by X-ray diffraction methods: C%H2,IN2Sn, orthorhombic, space group Pbca with a = 19.212 (3) A, b = 25.540 (8) A, c = 9.482 (1) A, and 2 = 8, final R = 0.052 for 1798 observed reflections. The tin center has a distorted-octahedral coordination geometry with mutual trans positions of the two C(l)naphthyl atoms, one of the coordinating nitrogen atoms and the iodine atom, and the other coordinating nitrogen atom and the methyl group at tin. The length of the Sn-N bond trans to the iodine atom is in the normal range a~ expected for a Sn-N coordination bond (2.53 (1) A) while the Sn-N bond trans to the methyl group is extremely long (3.10 (1) A). 'H, '%, and gSn NMR spectra of these triorganotin halides show that, at low temperature in solution, these compounds exist in two geometrically different forms, one aa found in the solid state and one with the two C(l)mpb++yl atoms, the two coordinating nitrogen atoms, and the methyl group at tin and the iodine atom in cis position. At higher temperatures a process involving interconversion between these two isomers becomes fast on the NMR time scale.

ChemInform Abstract: Synthesis and Structure of (2‐(4,4‐Dimethyl‐2‐oxazoline)‐5‐ methylphenyl)methylphenyltin Bromide. A Novel Triorganotin Halide Having a Configurationally Stable Chiral Tin Center.

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Synthesis and structure of [2-(4,4-dimethyl-2-oxazoline)-5-methylphenyl]methylphenyltin bromide. A novel triorganotin halide having a configurationally stable chiral tin center

Reaction of [2-(4,4-dimethyl-2-oxazoline)-5-methylphenyl]copper with dimethyltin dibromide or methylphenyltin dibromide affords [2-(4,4-dimethyl-2-oxazoline)-5-methylphenyl]dimethyltin bromide ( 1) and [2-(4,4-dimethyl-2-oxazoline)-5-methylphenyl]methylphenyltin bromide ( 2), respectively. The crystal structure of 2 has been determined by X-ray diffraction methods. C 19H 22BrNOSn is monoclinic, space group P2 t/ a with a = 18.1258(9), b = 11.5704(11), c = 9.5315(6) Å, β = 95.143(6)° and Z = 4, final R = 0.038 for 2760 observed reflections. As a result of intramolecular coordination of the nitrogen atom of the oxazoline ring to the tin atom, the geometry about tin in 1 is trigonal bipyramidal. The carbon ligands are at the equatorial sites, while the more electronegative nitrogen and bromine atoms are at the axial positions. An 1H NMR spectroscopic study showed that in solution the chiral tin center is configurationally stable up to 120°C )the highest temperature studied).