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.     

Syntheses,characterizations, and crystal structures of tri‐ and diorganotin (IV) derivatives with 2‐mercapto‐5‐methyl‐1,3,4‐thiadiazole

A series of organotin(IV) complexes with 2‐mercapto‐5‐methyl‐1,3,4‐thiadiazole (HL) of the type R₃ Sn(L) (R = Me 1 ; Bu 2 ; Ph 3 ; PhCH₂ 4 ) and R₂Sn(L)₂ (R = CH₃ 5 ; Ph 6 ; PhCH₂ 7 ; Bu 8 ) have been synthesized. All complexes 1–8 were characterized by elemental analysis, IR,¹H, ¹³ C, and ¹¹⁹Sn NMR spectra. Among these, complexes 1 , 3 , 4 , and 7 were also determined by X‐ray crystallography. The tin atoms of complexes 1 , 3 , and 4 are all penta‐coordinated and the geometries at tin atoms of complexes 3 and 4 are distorted trigonal–bipyramidal. Interestingly, complex 1 has formed a 1D polymeric chain through Sn and N intermolecular interactions. The tin atom of complex 7 is hexa‐coordinated and its geometry is distorted octahedral. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:353–364, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20215     

Zur Reaktivität von intramolekular basenstabilisierten Zinn(II)-Verbindungen mit Halogenen,Zinntetrachlorid und Chloroform

Reactivity of Intramolecular Basestabilized Tin(II) Compounds with Halogens, Tin Tetrachloride, and Trichloromethane Intramolecular basestabilized tin(II) compounds of the type RN(CH₂CH₂Y)₂Sn (Y = O, S and R = Me, t-Bu) react with halogens, tin tetrachloride, and trichloromethan at room temperature by oxydative addition reaction to tin(IV) derivatives. These compounds are characterized by n.m.r. investigations and by Mössbauer studies.     

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.     

Preparation and structures of [2‐(dimethylamino)phenyl]diorganotin(IV) acetates substituted with organophosphorus groups in the α‐position of the acetate ligand

Organotin(IV) carboxylates R₂L^NCSnOC(O)CH₂P(E)Ph₂, where L^NC is an N‐chelating 2‐(dimethylamino)phenyl group, and R/E = Ph/void (1a), Ph/O (1b), Ph/S (1c), Me/void (2a), Me/O (2b) and Me/S (2c), were synthesized, characterized by ¹H, ¹³C, ³¹P and ¹¹⁹Sn NMR, IR and MS spectra, and the solid‐state structures of 1b, 1c, 2b and 2c were determined by single‐crystal X‐ray diffraction. Spectral and structural data showed that the compounds are monomeric in CDCl₃ solution and the solid state, with the organophosphorus groups in the α‐position of the monodentate carboxylate ligands not interacting with the tin atom. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis,structure, and reactivity of germanium-containing derivatives of substituted diethanolamines

The reaction of dialkanolamines RN(CH₂CH₂O)(CHR’CHR’OH) (R = Me, Ph, PhCH₂; R’ = H, Ph) with tetraethoxygermane gives either 2,2-diethoxy-1,3,6,2-dioxazagermocanes RN(CH₂CH₂O)(CHR’CHR’O)Ge(OEt)₂ or 1,7,9,15-tetraoxa-4,12-diaza-8-germaspiro[7.7]pentadecanes [RN(CH₂CH₂O) (CHR’CHR’O)]₂Ge depending on the reactant ratio. The chemical behavior of the obtained compounds in substitution reactions at germanium was studied. The product structure was confirmed by elemental analysis data and ¹H, ¹³C, and ¹⁹F NMR spectroscopy. The cyclotrigermanoxane [MeN(CH₂CH₂O)₂GeO]₃ was studied by X-ray diffraction.     

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 .     

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.     

Monomere Tripod–Zink-Thiolat-Komplexe

Monomeric Tripod–Zinc Thiolate Complexes Reaction of the pyrazolylborate-zinc complex Tp^Cum,MeZn–OH with the corresponding thiols yielded the stable complexes Tp^Cum,MeZn–SR ( 1 : R = Ph, 2 : R = CH₂–Ph, 3 : R = CH₂–CH₂–Ph) which are further representatives of this class of compounds. Using the ligand tris(benzimidazolylmethyl)amine (BIMA), zinc perchlorate, and the corresponding sodium thiolates, the cationic complexes (BIMA)Zn–SR (R = Ph, CH₂Ph) were obtained, which were isolated as [(BIMA)Zn–S–Ph] BPh₄ ( 4 ) and [(BIMA)Zn–S–CH₂Ph] ClO₄ ( 5 ). A structure determination of 4 confirmed the pseudotetrahedral coordination geometry for this new type of compounds.     

Synthesis and Structural Characterization of Some Novel Trialkylsilyl‐substituted Lithium Benzyl Complexes [Li(tmeda)][CHRSiMe2R′] (R = Ph, 3,5‐Me2C6H3; R′ = Me,tBu, Ph)

The reactions of PhCH₂SiMe₃ ( 1 ), PhCH₂SiMe₂^tBu ( 2 ), PhCH₂SiMe₂Ph ( 3 ), 3,5‐Me₂C₆H₃CH₂SiMe₃ ( 4 ), and 3,5‐Me₂C₆H₃CH₂SiMe₂^tBu ( 5 ) with ⁿBuLi in tetramethylethylenediamine (tmeda) afford the corresponding lithium complexes [Li(tmeda)][CHRSiMe₂R′] (R, R′ = Ph, Me ( 6 ), Ph, ^tBu ( 7 ), Ph, Ph ( 8 ), 3,5‐Me₂C₆H₃, Me ( 9 ), and 3,5‐Me₂C₆H₃, ^tBu ( 10 )), respectively. The new compounds 5 , 7 , 8 , 9 and 10 have been characterized by ¹H and ¹³C NMR spectroscopy, compounds 7 , 8 and 9 also by X‐ray structure analysis.     

6-(N-Methyl)aza-2,10-dithia-1-stanna(II)-bicyclo[4,4,01,6]decan – ein Zehnring mit transannularer Zinn-Stickstoff-Wechselwirkung

6-(N-methyl)aza-2,10-dithia-1-stanna(II)-bicyclo[4.4.0^1,6]decane – a Ten-membered Ring with a Transannulare Tin-Nitrogen Interaction The reaction of tin(II) butoxide with N-methyl-bis(γ-mercaptopropyl)amine in toluene leads to the title compound in good yield. Its structure is investigated by ¹H-, ¹³C-, and ¹¹⁹Sn-n.m.r. spectroscopy and mass spectrometry.     

Organtin complexes of 2,5‐dithiobiurea (H2dtbu): The crystal structures of (Ph3Sn)2(dtbu) and [(n‐Bu)2SnCl]2(dtbu)

A series of organotin(IV) complexes of two types, [R₃Sn]₂(dtbu) (R = PhCH₂ 1 , Ph 2 , n‐Bu 3 , H₂dtbu = 2,5‐dithiobiurea), [R₂SnCl]₂(dtbu) (R = PhCH₂ 4 , Ph 5 , n‐Bu 6 ) have been synthesized and characterized by elemental analysis, IR, and NMR (¹H, ¹¹⁹Sn) spectroscopy. The structures of 2 and 6 have been determined by X‐ray crystallography. Crystal structures show that both complexes 2 and 6 are the symmetric dinuclear unit. Interestingly, supramolecular structures show that complex 2 has formed a linear chain through N H⋅⋅⋅S hydrogen bonding and 6 has formed a two‐dimensional network in perfect bc plane connected through N H⋅⋅⋅Cl hydrogen bonding and nonbonded S⋅⋅⋅S interactions. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:435–442, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20456     

Preparation and Conformation of Organo‐Bridged Bis[tris(arylchalcogenolato)tin] Compounds – An Experimental and Quantum Chemical Study

Seven organo‐bridged bis[tris(arylchalcogenolato)tin] compounds with the general formulae (R′E)₃Sn–R–Sn(ER′)₃ (R = –(CH₂)₄–, 1,4‐bis(methyl)benzene, 4,4′‐bis(methyl)biphenyl; R′ = Ph, 1‐Np, 2‐Np; E = S, Se) were synthesized and characterized by means of X‐ray diffractometry as well as NMR spectroscopy. Three different conformations of the arylchalcogenolato groups ER′ with respect to the bridging group R were rationalized and explained by means of quantum chemical investigations.     

Synthesis,molecular structure and stereoisomerization of 2-phosphinyl and 2-phosphonylethyl diorganotin halides

Functionally substituted triorganotin halides V–IX of type R₂Sn(X)(CH₂)₂P(O)PhR′ (R = Me, t-Bu; Rt? = OEt, t-Bu; X = Cl, Br) have been synthesized by halogen cleavage of the corresponding tetraorganotin compounds R₂R²Sn(CH₂)₂P(O)PhR′ (R² = Me or Ph), I–IV. The solid state structure of Me₂Sn (Br) (CH₂)₂P(O)PhBu-t (IX), determined by X-ray diffraction, shows a distorted trigonal-bipyramidal structure at the tin atom, with intramolecular coordination of the PO group. Spectroscopic data are in agreement with such a structure in solution for compounds V–IX. Upon varying the temperature, concentration or solvent in solutions of compounds V–IX a stereoisomerization is observed. On the basis of NMR ¹H, ¹³C, ³¹P, ¹¹⁹Sn), IR and conductivity studies, it is suggested that this stereoisomerization involves a hexacoordinated transition state at the tin atom.     

Synthesis,properties and crystal structural characterization of diorganotin(IV) derivatives of 2‐mercapto‐6‐nitrobenzothiazole

The diorganotin(IV) dichlorides R₂SnCl₂ (R: Ph, PhCH₂ or n‐Bu) react with 2‐mercapto‐6‐nitrobenzothiazole (MNBT) in benzene to give [Ph₂SnCl(MNBT)] ( 1 ), [(PhCH₂)₂Sn(MNBT)₂] ( 2 ) and [(n‐Bu)₂Sn(MNBT)₂] ( 3 ). The three complexes have been characterized by elemental analysis and IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopies. X‐ray studies of the crystal structures of 1 , 2 and 3 show the following. The tin environment for complex 1 is distorted cis‐trigonal bipyramid with chlorine and nitrogen atoms in apical positions. The structure of complex 2 is a distorted octahedron with two benzyl groups in the axial sites. The geometry at the tin atom of complex 3 is that of an irregular octahedron. Interestingly, intra‐molecular non‐bonded Cl…S interactions and S…S interaction were recognized in the crystallographic structures of 1 and 3 respectively. As a result, complex 1 is a polymer and complex 3 is a dimer. Copyright © 2003 John Wiley & Sons, Ltd.     

Some mixed cyclopentadienyl–indenyl zirconium complexes with PhCH2 or PhCH2CH2 substituents in ethylene polymerization

(RCp)(R′Ind)ZrCl₂ complexes 1 – 6 (Cp = cyclopentadienyl; Ind = indenyl; 1 , R = PhCH₂ and R′ = H; 2 , R = PhCH₂ and R′ = PhCH₂; 3 , R = PhCH₂CH₂ and R′ = H; 4 , R = PhCH₂CH₂ and R′ = PhCH₂; 5 , R = o‐Me? PhCH₂CH₂ and R′ = H; 6 , R = o‐Me? PhCH₂ and R′ = H) were synthesized and characterized with ¹H NMR, elemental analysis, mass spectrometry, and infrared spectroscopy. Their catalytic behaviors were compared with those of (Et₃SiCp)(PhCH₂CH₂Cp)ZrCl₂, (PhCH₂Cp)₂ZrCl₂, (PhCH₂‐ CH₂Cp)₂ZrCl₂, (o‐Me? PhCH₂CH₂Cp)₂ZrCl₂, and (Ind)₂ZrCl₂ in ethylene polymerization in the presence of methylaluminoxane. Complex 5 showed high activity up to 2.43 × 10⁶ g of polyethylene (PE)/mol of Zr h, and complex 4 produced PE with bimodal molecular weight distributions. The methyl group at the 2‐position of phenyl in complex 5 increased the activity greatly. The relationships between the polymerization results and the structures were analyzed with NMR spectral data. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1261–1269, 2005     

Zur Umsetzung von Bis(2-mercaptoethyl)phosphinen mit Organozinn-Verbindungen Molekülstruktur eines zinnhaltigen Sechzehnringes

Reaction of Bis(2-mercaptoethyl)phosphines with Organotin Compounds. Molecular Structure of a Tin Containing Sixteen-membered Ring The reaction of bis(2-mercaptoethyl)phosphine with di-t-butyltin dimethoxide yields mixture of oligomers of the type [t-Bu₂Sn(SCH₂CH₂)₂Pr]_n (R ? Me, Ph) from which the trans-configurated dimers (n = 2) have been isolated. By the reaction with sulphur and selenium, respectively, these dimers were transformed to the corresponding thioxo and selenoxo derivatives. The sixteen-membered ring trans-[t-Bu₂Sn(SCH₂CH₂)₂P(S)Ph]₂ crystallizes in the space group P2₁/n with the unit cell dimensions a 1350.9, b 1310.2, c 1500.3 pm, β 96.36° and does not exhibit any intramolecular Sn? P interaction: The 1,5-diorgano-1-chloro-5-elementa-1-stanna(IV)-bicyclo-[3.3.0^1,5]octanes R(Cl)Sn(SCH₂CH₂)₂E ( 6 , R ? Ph, E ? PPh; 7 , R ? Ph, E ? NMe) have been prepared from the corresponding sodium dithiolates and phenyltrichlorostannane. The transannulare Sn? P and Sn? N interactions in 6 and 7 are confirmed by ³¹P and ¹¹⁹Sn NMR investigations.     

Diorganotin(IV) complexes of 2,5‐dithiobiurea (H2dtbu). The crystal structures of Me2Sn(dtbu) and Ph2Sn(dtbu)

The diorganotin(IV) complexes, R₂Sn(dtbu) (R = Me 1 , n‐Bu 2 , Ph 3 , PhCH₂ 4 ; H₂dtbu = 2,5‐dithiobiurea), have been synthesized and characterized by IR, ¹H, and ¹¹⁹Sn NMR spectroscopy. The structures of 1 and 3 have been determined by X‐ray crystallography. Crystal structures show that both complexes 1 and 3 consist of molecules in which the bideprotonated ligand is N,S,S‐bonded, and the tin atom exhibits distorted pentacoordination with small differences between the methyl and phenyl derivatives in bond distances and bond angles. The unusual coordination mode of the dtbu²⁻ anion creates four‐ and five‐membered chelate rings. Moreover, the packing of complexes 1 and 3 are stabilized by the hydrogen bonding. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:93–98, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20173     

Syntheses,characterizations, and crystal structures of organotin(IV) chloride complexes with 4,4′‐bipyridine

The organotin(IV) chlorides R_nSnCl_4−n (n = 3, R = Ph, PhCH₂, n−Bu; and n =2, R = n−Bu, Ph, PhCH₂) react with 4,4′‐bipyridine (4′4‐bpy) to give [(Ph₃SnCl)₂(4,4′‐bpy)_1.5(C₆H₆)_0.5] ( 1 ), [(PhCH₂)₃‐ SnCl]₂ (4,4′‐bpy) ( 2 ), [(n−Bu)₃SnCl]₂(4,4′‐bpy) ( 3 ), [(n−Bu)₂SnCl₂(4,4′‐bpy)] ( 4 ), [Ph₂SnCl₂(4,4′‐bpy)] ( 5 ), and [(PhCH₂)₂SnCl₂(4,4′‐bpy)] ( 6 ). The new complexes have been characterized by elemental analyses, IR, ¹H, ¹³C, ¹¹⁹Sn NMR spectroscopy. The structures of ( 1 ), ( 2 ), ( 4 ), and ( 6 ) have been determined by X‐ray crystallography. Crystal structures of ( 1 ) and ( 2 ) show that the coordination number of tin is five. In complex ( 1 ), two different molecules exist: one is a binuclear molecule bridged by 4,4′‐bpy and another is a mononuclear one, only one N of 4,4′‐bpy coordinate to tin. Complex ( 2 ) contains an infinite 1‐D polymeric binuclear chain by weak Sn…Cl intermolecular interactions with neighboring molecules. In the complexes ( 4 ) and ( 6 ), the tin is six‐coordinate, and the 4,4′‐bpy moieties bridge adjacent dialkyltin(IV)dichloride molecules to form a linear chain. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:338–346, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20016     

Mechanism of the Nickel-Catalyzed Electrosynthesis of Ketones by Heterocoupling of Acyl and Benzyl Halides

Summary.  The mechanism of the nickel-catalyzed electrosynthesis of ketones by heterocoupling of phenacyl chloride and benzyl bromide has been investigated by fast scan rate cyclic voltammetry with [Ni(bpy)²⁺ ₃](BF₄ ⁻)₂ as the catalytic precursor (bpy = 2,2{−}{ bipyridine}). The key step is an oxidative addition of Ni⁰(bpy) (electrogenerated by reduction of the Ni(II) precursor) to PhCH₂Br whose rate constant is found to be 10 times higher than that of PhCH₂COCl. The complex PhCH₂Ni^IIBr(bpy) formed in the oxidative addition is reduced at the potential of the Ni^II/Ni⁰ reduction by a two-electron process which affords an anionic complex PhCH₂Ni⁰(bpy)⁻ able to react with PhCH₂COCl to generate eventually the homocoupling product PhCH₂COCH₂Ph. The formation of the homocoupling product PhCH₂COCOCH₂Ph is prevented because of the too slow oxidative addition of Ni⁰(bpy) to PhCH₂COCl compared to PhCH₂Br. The formation of the homocoupling product PhCH₂CH₂Ph is also prevented because PhCH₂Ni⁰(bpy)⁻ does not react with PhCH₂Br. This explains why the electrosynthesis of the ketone can be performed selectively in a one-pot procedure, starting from an equal mixture of PhCH₂COCl and PhCH₂Br and a nickel catalyst ligated by the bpy ligand. Received June 27, 2000. Accepted July 11, 2000