Zur Reaktivität von intramolekular basenstabilisierten Zinn(II)- Verbindungen mit Mercaptanen,Disulfiden und Peroxiden

Reactivity of Intramolecular Basestabilized Tin(II) Compounds with Mercaptanes, Disulfides, and Peroxides New pentacoordinated stannaocanes can be obtained in good yields by the reaction of intramoleculare basestabilized tin(II) compounds of the typ E(CH₂CH₂S)₂Sn (E = NMe, S) with mercaptanes RSH (R = Ph, PhCH₂) and disulfides RSSR (R = Ph, PhCH₂). The redistributation of the main product proceeds as a byreaction. The resulting spirocompounds and tin tetrathiolates have been determined by ¹¹⁹Sn-n.m.r. spectroscopy. The reaction of the tin(II) compound with dibenzoylperoxide only results in the addition product. All new compounds are characterized by ¹H-, ¹³C- and ¹¹⁹Sn-n.m.r. measurements and partially by i.r. investigations.     

5-Thia-2,8(N-alkyl)diaza-1-stanna(II)-bicyclo[3.3.01,5]octane – Intramolekular basenstabilisierte Diazastannylene

5-Thia-2,8(N-alkyl)diaza-1-stanna(II)-bicyclo[3.3.0^1,5]octanes – Intramolecular Basestabilized Diazastannylenes The title compounds are obtained by transamination of tin(II) dimethylamide with compounds of the type S(CH₂CH₂N(R)H)₂ (R = t-Bu, i-Pr) or by reaction of tin(II) chloride with the corresponding lithium amides. The monomeric structure is proved by temperature dependend ¹H-, ¹³C-, ¹¹⁹Sn n.m.r., and Mössbauer measurements.     

Synthesis and reactivity of ω-haloalkyltin compounds

ω-Haloalkyltin trihalides, X(CH₂)_nSnX₃ (n ≧ 3; X = halogen) can readily be prepared in high yields by the direct reaction of stannous halides with α,ω-dihaloalkanes, catalysed by trialkylantimony compounds. The compounds are versatile starting materials for the synthesis of a variety of ω-functionallysubstituted organotin compounds R_3-mX_mSn(CH₂)_n Y (R = alkyl, phenyl; m = 0-3; X = Cl, Br, O; Y = Br, NMe₂, NEt₂, COOH, CHOHR, R₃Sn). ¹H-NMR spectral data for a series of such compounds are presented. The trends observed in the chemical shifts and the ¹¹⁹Sn—methyl proton coupling constants of Me_3-m Br_mSn(CH₂)_nBr (m = 0-3; n = 3-5) are discussed in terms of inductive effects. Intramolecular coordination between the ω-bromine atom and tin could not be demonstrated.     

Methyl-Dichlorophosphate von Zinn und Blei

Methyl Dichlorophosphates of Tin and Lead The compounds (CH₃)₃M(O₂PCl₂) (I), (M = Sn, Pb) and (CH₃)₂Sn(O₂PCl₂)₂ (II), formed by the reaction of the corresponding methyltin and methylleadchlorides with P₂O₃Cl₄ are described. The IR and Mössbauer spectra suggest that the tin compounds are polymerized through O? P? O bridges, whereby (I) and (II) contain metal atoms with coordination numbers five (D_3h) and six (D_4h), respectively.     

Oxidative addition reactions of dicyclopentadienyltin(II) and of tin(II) bis(acetylacetonate) with organic halides. The preparation of compounds of the type RSn(acac)2X

Oxidative addition reactions of tin(II) bis(acetylacetonate) with organic halides provide a route to new monoorganotin(IV) bis(acetylacetonate) halides. Dicyclopentadienyltin(II) undergoes oxidative addition with methyl iodide, diiodomethane and ethyl bromoacetate, but with allyl bromide, benzyl bromide and triphenylmethyl bromide carbon—carbon coupling reactions and the formation of the corresponding cyclopentadienyltin(II) halide take place. Some of the reactions are accelerated by light. NMR spectroscopic data show that the RSn(acac)₂X compounds have a cis-configuration. The compounds YCH₂Sn(acac)₂X (e.g. Y = I, CHCH₂, COOEt) provide the first examples of diastereo-topic non-equivalence of methylene protons in organotin compounds containing a hexacoordinate chiral tin centre.     

5-Aza(Oxa,Thia)-2,8-dithia-1-stanna(II)-bicyclo[3.3.01,5]octane Intramolekular basenstabilisierte Stannylene

5-Aza(oxa, thia)-2, 8-dithia-1-stanna(II)-bicyclo[3.3.0^1,5]octanes — Intramolecular Stabilized Stannylenes By the reaction of tin(II) butoxide with mercaptanes of the general type E(CH₂? CH₂SH)₂ (E ? N-t-Bu, NMe, O, S) at temperatures up to 50°C the 5-aza(oxa, thia)-2, 8-dithia-1-stanna(II)-bicyclo[3.3.0^1,5]octanes I—IV are obtained in high yields. The compounds are monomeric in solution. Contrary at higher reaction temperatures (80°C) the spiro-compounds of the type [E(CH₂CH₂S)₂]₂Sn ( V—VIII ) are formed. Some typical stannylene reactions of I—IV with BF₃, Cr(CO)₆, Br₂, and PhS? SPh show the high reactivity of the compounds. Their structure is investigated by ¹H, ¹³C, and ¹¹⁹Sn n.m.r., i.r., and Mössbauer spectroscopy.     

1-Organo-diptych-thiaphosphastanno(II)-lidine

Bei der Umsetzung von Zinn(II)-dialkoxiden mit den Phosphinen RP(CH₂CH₂SH)₂ (R ? Me, Et, t? Bu, Ph) werden Stannylene des Typs Sn(S? CH₂? CH₂)₂PR erhalten, die in Lösung monomer vorliegen. Mittels NMR-Spektroskopie und Massenspektroskopie wird eine intramolekulare Phosphor-Zinn-Koordination nachgewiesen. Die Verbindungen besitzen folglich eine bicyclische Struktur. 1-Organo-diptych-thiaphosphastanno(II)-lidines The reaction of tin(II) dialkoxides with phosphines RP(CH₂CH₂SH)₂ (R ? Me, Et, t? Bu, Ph) gives stannylenes of the type Sn(S? CH₂? CH₂)₂PR, which are monomeric in solution. An intramolecular phosphorus?tin coordination is proved by nmr and mass spectroscop. Therefore the compounds must have a bicyclic structure.     

Verbindungen des Germainums und Zinns. 17. Alkylarylstannylen-Komplexe des Chroms und Molybdäns ohne Donorstabilisierung

Compounds of Germanium and Tin. 17 [1]. Alkylarylstannylene Complexes of Chromium and Molybdenum without Donor Stabilization Reaction of the complexes [(OC)₅M(THF)], M = Cr, Mo, with the alkylarylstannylene RR′Sn: R = 2,4,6-tBu₃C₆H₂, R′ = CH₂C(CH₃)₂-3,5-tBu₂C₆H₂, provides the donor-free stannylene complexes [(OC)₅Cr?SnRR′] ( 6 ) and [(OC)₅Mo?SnRR′] ( 8 ), respectively. The X-ray structure analyses of the isotypic compounds 6 and 8 reveal the three coordinate tin atoms in strictly planar environments and acute CSnC angles of 91.2° ( 6 ) and 91.3° ( 8 ).     

C-Stannylmethylierte N-Acetyl- und N-Formyl-aminomalonsäure-Derivate

C-Stannylmethylated N-Acetyl- and N-Formyl-aminomalonic Acid Derivatives Tin compounds of the type Me₃SnCH₂C(NHCOR) · (COOEt)₂ ( 1 : R = CH₃; 2 : R = H) are synthesized by reaction of acylaminomalonates with iodomethyl trimethylstannane. The halogenation of 1 and 2 yields the halostannylsubstituted compounds Me_3?nX_nSnCH₂C(NHCOR)(COOEt)₂ 3–6 (R = Me, H; n = 1, 2; X = Cl, Br). The decarbethoxylation (KRAPCHO reaction) of 1 and 2 gives ethyl 3 -(trimethylstannyl)-N-acyl alaninates ( 7 and 8 ). With one equivalent KOH 1 and 2 are transformed into the monoethyl malonates of the type Me₃SnCH₂C(NHCOR)(COOH)(COOEt) ( 9 : R = CH₃), which convert simultaneously under decarboxylation into 7 and 8 and by cyclisation under elimination of methane into the 1,2-oxastannolane derivatives 10 and 11 . IR, NMR data and the determination of the crystal structure reveal for MeBr₂SnCH₂C(NHCOCH₃)(COOEt)₂ ( 5 ) hexacoordinated tin by intramolecular coordination of the amide-CO and one of the ester-CO groups.     

Synthese von 1, 2-annelierten 1, 4-Benzodiazepinen und 4, 1-Benzoxazepinen

The syntheses of 1, 2-annelated 1, 4-benzodiazepines (IV, Y = N) and 4, 1-benzoxazepines (IV, Y = 0) are described (Scheme 1). The key step is a nucleophilic aromatic substitution of 2-substituted piperazines (II, Z = N? CH₃), piperidines (II, Z = CH₂) or pyrrolidines (II, Z= (CH₂)₀) with activated aryl halides (I).     

Fluoridolyse von Diphosphorylverbindungen

Fluoridolysis of Diphosphoryl Compounds The behaviour of diphosphoryl compounds [X₂(O)P]₂Y in fluoridolysis reactions is decisively determined by the nature of the bridging group Y. In the cases of Y = NH and CH₂ and X = Cl [F₂P(O)]₂N^? and [F₂P(O)]₂CH₂ are obtained quantitatively. For Y = NPh, O, and CH₂ the formation of phosphorylated pentafluorophosphates [F₅P? Y? POX₂]^? is observed. Amido and ester derivatives containing fluorine (see table 2) are obtained from the corresponding chloro compounds by Cl/F exchange. Fluoridolysis of the azadiphosphetidine 19 results in the formation of acyclic 19 a .     

Uber die Reaktionen der Hexacarbonyle der VI. Nebengruppe mit Zinn (II)- und Germanium (II)-halogeniden

On Reactions of Subgroup. VI. Hexacarbonyls with Tin(II) and Germanium (II) Halides The neutral complexes M(CO)₅SnX₂ and M(CO)₅GeCl₂ (M = Cr, Mo, W; X = Cl, Br, J) have been prepared by a photochemical reaction between M(CO)₆ and SnX₂, or CsGeCl₃ in THF. The reaction of these compounds with [N(CH₃)₄]X (X = Cl, Br, J) in THF was found to lead to a series of anions [M(CO)₅SnX₃]^? or [M(CO)₅GeCl₃]^? (M = Cr, Mo, W; X = Cl, Br, J), some of which have previously been prepared. The physical properties and IR-spectra of the above compounds are discussed.     

Synthesis and reactivity of novel cationic organonickel(II) compexes. X-ray structure of [bis(2-diphenylphosphinoethyl)phenylphosphinenickel-O-methylsulfinate]tetraphenylborate

Cationic tetracoordinate nickel(II) compounds containing a nickelcarbon σ bond with general formula [NiR(etp)]Y, (etp  bis(2-diphenylphosphinoethyl)phenylphosphine, PhP(CH₂CH₂PPh₂)₂; R = CH₃, CH₂C₆H₅, C₆H₅; Y = BPh₄, PF₆) were synthesized by reaction of the complexes [NiX(etp)]Y (X = halogen) with appropriate Grignard reagents.This type of organometallic complexes undergo insertion of sulfur dioxide into the NiC bond with formation of tetracoordinate O-sulfinate derivatives of nickel(II). The structure of [NiOS(O)CH₃(etp)]BPh₄ has been determined from three dimensional X-ray data collected by counter methods. The compound crystallized in the triclinic group P$\text{1}$ with cell dimensions a 16.726(4), a 15.350(4), c 11.632(3) Å, α 66.55(4), β 73.37(4), γ 74.75(4)°, Z = 2. The structure was refined by full matrix least-squares methods to a conventional R factor of 0.076. The coordination polyhedron has a distorted square planar geometry. The sulfinate group is linked to the metal through an oxygen atom.     

Anodic dissolution of tin in alcohols

Tin(II) alcoholates Sn(OR)₂ are formed upon the anodic galvanostatic dissolution of tin in alcohols in an undivided cell in the presence of minimum amounts of NaOAc as an electrolyte. Tin(II) alcoholates are easily hydrolyzed in air to form oxyhydroxide Sn₃O₂(OН)₂ used as an anode or its composite component in lithium cells.

     

On the mechanism of polymerization of cyclic esters induced by tin(II) octoate

Mechanism of initiation and propagation in polymerization of ϵ‐caprolactone and L,L‐dilactide induced with tin(II) octoate (Sn(Oct)₂) and Sn(Oct)₂/n‐butyl alcohol system is presented. Tin(II) alkoxide bond formation is required in reaction of Sn(Oct)₂ with hydroxyl group containing compound to form a true initiator. Then tin(II) alkoxide end group is an active centre in the further propagation.     

Darstellung und NMR-spektroskopische Charakterisierung von konfigurationsstabilen Diorganozinn(IV)-Komplexen RPhSnL mit Zinn als chiralem Zentrum

Synthesis and Characterization of Configurationally Stable Diorganotin(IV) Complexes with Tin as a Chiral Centre Contrary to the high optical stability of tetraorganotin compounds most heteroleptic organic tin compounds are configurationally instable. We report the synthesis and the characterization of some new enantiomeric and diastereomeric diorganotin(IV) complexes of stable configuration with tin as a chiral centre. The stabilization of the chiral tin atom was realized by complexation with tridentate diacidic esterhydrazone ligands H₂L, which prevent an interconversion at the stereogenic centre. Multinuclear NMR-studies in solution demonstrate, that the configuration of the chiral tin center is configurationally stable up to 160°C. The molecular structure of the complexes Neophyl-phenyl-tin-2[(2-methyl-mercaptothiocarbonyl)-hydrazono]propionate II b and (2-Methyl-butyl-1-yl)-phenyl-tin-[S-methyl-β-N-(2-salicylmethylidene)thiocarbazat] III g have been determined by single crystal X-ray diffraction analysis.     

Synthesis,structure and cytotoxic activity of diethyltin N‐[(2‐oxyphenyl)methylene]phenylalaninates

Four new diethyltin N‐[(2‐oxyphenyl)methylene]phenylalaninates, (CH₃CH₂)₂Sn[2‐O‐3‐X‐5‐YC₆H₂CH?NCH(CH₂Ph)COO] (X, Y = H, H, 1 ; H, Br, 2 ; H, OCH₃, 3 ; Br, Br, 4 ), have been synthesized and characterized using elemental analysis and infrared and NMR (¹H, ¹³C and ¹¹⁹Sn) spectra. The crystal structures of 1 , 2 , 3 , 4 have been determined. Compounds 1 and 2 have a 12‐membered macrocyclic structure with a trimeric [Sn₃O₆C₃] core. Each tin atom is six‐coordinated in distorted [SnC₂NO₃] octahedral geometry. Compound 3 is a centrosymmetric weak dimer in which the two tin centers are linked by two asymmetric Sn? O???Sn bridges involving the phenolic oxygen of the ligand and two Sn???O interactions from ether oxygen of the adjacent ligand. The coordination geometry of the tin atom can be described as a distorted pentagonal bipyramid with two ethyl groups in axial positions. Compound 4 is a novel binuclear tin complex, formed by the carboxylate of a ligand asymmetrically bridging two tin atoms, which contains a five‐coordinated tin and a six‐coordinated tin. Bioassay results have shown that the compounds have weak in vitro activity against two human tumor cell lines, A549 and CoLo205. Copyright © 2016 John Wiley & Sons, Ltd.     

Reaction of 3-dimethylamino-(1,1 -dimethyl) propyl magnesium chloride with tin (IV) and tin (II) chlorides. Stabilization of a SnCl+ cation in the new tin cluster [Me2NCH2CH2C(Me2)SnCl]3 · SnCl2

The reactions of the functional Grignard reagent Me₂ NCH₂CH₂C(Me₂)MgCl (4) with tin tetrachloride, dimethyltin dichloride, and tin (II) chloride are described. From the reactions the compounds bis(3-dimethylamino-1,1-dimethylpropyl) tin dichloride, [Me₂NCH₂CH₂C(Me₂)]₂SnCl₂ (5) , dimethyl(3-dimethylamino-1,1-dimethylpropyl) chlorostannane, Me₂ClSnC(Me₂)CH₂CH₂NMe₂ (6) , 1,1,2,2-tetramethyl-1,2-bis(3-dimethylamino-1,1-dimethylpropyl) distannane,[Me₂SnC(Me₂)CH₂CH₂NMe₂]₂ (7) , 3-dimethylamino-(1,1-dimethyl)propyl tin (II) chloride, Me₂NCH₂CH₂C(Me₂)SnCl (8) , hexakis(3-dimethylamino-1,1-dimethylpropyl) cyclotristannane, {[Me₂NCH₂CH₂C(Me₂)]₂Sn}₃ (9a) , and the tin cluster [Me₂NCH₂CH₂C(Me₂)SnCl]₃ · SnCl₂ (10) have been isolated and characterized by means of multinuclear NMR and Mössbauer spectroscopy, and X-ray diffraction. 10 crystallizes in the trigonal space group P3₁ with the unit cell dimensions a 11.938, c 21.873 Å, V 2699.6 ų Z = 3. The structure was refined to a final R value of 0.064. 10 represents a tetranuclear cluster the skeleton of which is composed out of 4 Sn and a bridging Cl. Formally, the central tin atom is a SnCl⁺ cation stabilized by three stannylene units in a Ψ-trigonal bipyramidal environment. The tin-tin bond lengths are 288.2, 287.3 and 315.6 pm. The intramolecular Sn? N interactions amount to 242.8, 247.4 and 221.0 pm.     

Darstellung und Eigenschaften von Diorganyl-bis(seleninato-O,O′)-Komplexen des Bleis und Zinns

Preparation and Properties of Diorganyl-bis(seleninato-O,O′) Complexes of Lead and Tin The colourless, thermically stable diorganyl-bis(seleninato-O , O ′) complexes of lead and tin R₂E(O₂SeR′)₂[E = Pb (1) , Sn (2) ] are obtained by reaction of diorganyllead- and -tindichlorides R₂ECl₂ (R = C₆H₅, CH₃, C₂H₅, n-C₄H₉) with different sodiumseleninates R′SeO₂Na (R′ = C₆H₅, CH₃, C₂H₅) at 20°C. On the basis of their i.r., Raman, and Mößbauer spectra and their slightly solubility in all organic solvents a polymeric structure is supposed in which each two R′SeO₂ - ligands are linking two lead and tin atoms respectively (c.n. = 6) intermolecular (seleninato-O , O ′). The organic residues are in trans-position.     

Vier- und achtgliedrige metallhaltige Bor–Stickstoff-Heterocyclen. Bildung und Strukturen in Abhängigkeit von der Raumerfüllung der Substituenten

Four and Eight Membered Metal Containing Boron–Nitrogen-Heterocycles. Formation and Structures in Dependence on the Steric Requirement of their Substituents TripB(NRLi)₂ (Trip = 2,4,6-triisopropylphenyl, R = Me ( II a ), CH₂Me ( II b ), CHMe₂ ( II c ), CMe₃ ( II d ) reacts with dibromo(dimethyl)tin to give eight membered ( III a , III b ) and four membered metallacycles ( IV c and IV d ). If tetrahalides (GeCl₄, SnCl₄) are the reaction partners, the spiro compounds V c and VI d are obtained from II c and II d resp. The compounds are characterized by their m.s. and n.m.r. (¹H, ¹¹B, ¹³C, ¹⁹F, ¹¹⁹Sn) spectra and by elemental analyses. An X-ray structure analysis was performed for III a .