Reactivity of thallium tris[tris(pentafluorophenyl)germyl] mercurate

Metallic lithium and dibenzenechromium displace thallium from (R^f₃Ge)₃HgTl·1.5DME (R^f = C₆F₅, DME = 1,2-dimethoxyethane) to give (R^f₃Ge)₃HgLi·3DME and [(R^f₃Ge)₄Hg][Cr(C₆H₆)₂]₂, respectively. Reactions of thallium germylmercurate with halides of metals and organometallics in DME/EtOH solution produce ionic compounds of [(R^f₃Ge)₃Hg]^? M⁺ type, which (depending on “M”) (a) may be isolated as pure compounds, (b) disproportionate, (c) form covalent derivatives R^f₃Ge-m or (d) undergo alcoholysis. A general scheme for the reactions has been proposed.     

Synthesis and properties of trefoil-shaped tris(hexadehydrotribenzo[12]annulene) and tris(tetradehydrotribenzo[12]annulene)

[reaction: see text] Trefoil-shaped tris(hexadehydrotribenzo[12]annulene) possessing a substructure of the ultimate two-dimensional C(sp)-C(sp(2)) network, graphyne, and the related tris(tetradehydrotribenzo[12]annulene) were synthesized, and their ground- and excited-state properties were investigated.     

[Z]-1-[2-(三芳基锡基)乙烯基]环辛醇的合成和性质

本文用三苯基氢化锡、三对甲苯基氢化锡作为锡氢化试剂与1-乙炔基环辛醇进行反应, 合成了两个有机锡化合物: [Z]-1-[2-(三苯基锡基)乙烯基]环辛醇(1)和[Z]-1-[2-(三对甲苯基锡基)乙烯基]环辛醇(2), 并测定了1的晶体结构。1和2分别与ICl, Br2, I~2反应, 得到六个有机锡一卤化物和三个有机锡二卤化物(3-11)。有机锡二卤化物6和一卤化物5与KOH乙醇溶液反应, 分别得到相应的锡氧化物和锡氢氧化物(12, 13)。有机锡二卤化物8分别与含氮双齿配体[2,2'-联吡啶(Bipy),5-硝基-1,10-邻菲罗啉(Nphen),8-羟基喹啉(Oxin)]反应, 得到三个相应的配合物(14-16)。十六个新化合物通过元素分析、锡含量测定、IR、^1H NMR测定对其结构进行了表征, 同时提出了1和2的生成反应历程。     

Metallierung von Triisopropylsilylarsan durch Bis(tetrahydrofuran)calcium‐bis[tris(trimethylsilylmethyl)zinkat]

Metalation of Triisopropylsilylarsane with Bis(tetrahydrofuran)calcium‐bis[tris(trimethylsilylmethyl)zincate] The transmetalation of bis(trimethylsilylmethyl)zinc with distilled calcium in THF yields bis(tetrahydrofuran)calcium bis[tris‐(trimethylsilylmethyl)zincate] ( 1 ). The trialkylzincate anion appears as a bidentate ligand with Ca‐C‐Zn three‐center‐bonds. The CaC bond lengths show values of 265.5(2) and 271.7(2) pm. The metalation of triisopropylsilylarsane gives tetrakis(tetrahydrofuran)calcium [1, 3‐bis(triisopropylsilylarsanyl)‐2, 4‐bis(triisopropylsilyl)‐1, 3‐dizinca‐2, 4‐diarsacyclobutane‐2, 4‐diide] ( 2 ). The central moiety is a sligthly distorted trigonal As₂CaZn₂ bipyramid with the arsenic atoms in apical positions. The mean Ca‐As bond lengths lie with a mean value of 291.4 pm in the charakteristic region for calcium bis‐(arsanides).     

The complex of dicarbonyl(methylcyclopentadienyl)molybdenum with carbonyl(cyclopentadienyl)nitrosyl[tris(phenylacetylenide)stannyl]manganese: Synthesis and molecular formula

A reaction of CpMn(CO)(NO)Sn(C=CPh)₃ (I) with [Cp′Mo(CO)₂]₂ (Cp′ = MeC₅H₄) gave CpMn(CO)(NO)Sn(C=CPh)₃[Cp′Mo(CO)₂]₂ (II) as dark red prismatic crystals. The molecular structure of complex II was determined by X-ray diffraction study. Complex II contains the Mo-Mo bond (2.9799(5) Å), which is perpendicular to the coordinated C=C bond. The latter is longer (1.371(5) Å) than free acetylenide fragments (1.190(5) and 1.198(5) Å). In addition, the angle Sn-C=C for the coordinated C=C bond is smaller (134.1(3)°) than that in free fragments (173.5(4)° and 171.9(4)°). The Mn-Sn bond length in complex II (2.5662(7) Å) is close to that in complexI (2.5328(17) Å) and is much shorter than the sum of the corresponding covalent radii (2.78 Å). The Sn-C bond (2.108(4) Å) in the acetylenide fragment π-bound to two Mo atoms (average Mo-C, 2.19 Å), as well as the other Sn-C bonds (2.119(4) and 2.135(4) Å), remains virtually the same as in complex I (average 2.105 Å).     

Reactions of tris(trimethylsilylmethyl)-stannyllithium with peroxides

Conclusions The reactions of tris(trimethylsilylmethyl)stannyllithium with tert-butyl peroxide, trimethyl(tertbutylperoxy)silane, triphenyl(tert-butylperoxy)germane, benzoyl peroxide and dicyclohexyl peroxydicarbonate proceed with a heterolytic cleavage of the peroxide group. In the unsymmetrical peroxides the less shielded oxygen atom is subjected to attack.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2776–2778, December, 1973.     

Synthesis and reactions of [tris(trimethylsilyl)methyl]ethyl dichlorosilane

The crowded dichlorosilane TsiSiEtCl₂, (1), (Tsi = (Me₃Si)₃C) was prepared from the reaction between EtSiCl₃ and TsiLi, then it was reduced with LiAlH₄ to give TsiSiEtH₂, (2). The hydride (2) was then treated with two equivalents of ICl/CCl₄ or Br₂/CCl₄ to produce TsiSiEtI₂, (3), and TsiSiEtBr₂, (4), respectively. The reaction of compound (2) with one equivalent of ICl/CCl₄ gives TsiSiEtHI, (5). This product reacted with H₂O/dioxane in the presence of AgClO₄ or with dry MeOH to produce TsiSiEtHOH, (6), and TsiSiEtHOMe, (7), respectively. The compound (3) reacted with H₂O in DMSO/CH₃CN to give TsiSiEt(OH)₂, (8), and the compound TsiSiEtIOMe, (9), was prepared from the reaction of the compound (7) with ICl/CCl₄. When the dichloride (1) was treated with NaOMe/MeOH it gave (Me₃Si)₂CHSiEt(OMe)₂. It is suggested that the reaction proceeds through an elimination-addition mechanism. The dichloride (1) was also treated with KSCN, NaN₃ or NaOCN in CH₃CN to give S_N2 substitution products. All the new products were characterized by FTIR, ¹H NMR, and ¹³C NMR spectroscopy, mass spectrometry and elemental analysis.     

Trichlorostannyl and tris(phenylacetylenide)stannyl complexes of manganese cyclopentadienylcarbonylnitrosyl: Synthesis and molecular structures

The heating of the ionic complex [CpMn(CO)₂(NO)]⁺SnCl₃-(I) in methylene chloride gives a neutral complex CpMn(CO)(NO)SnCl₃ (II). The latter reacts with lithium phenylacetylenide to yield a complex CpMn(CO)(NO)Sn(C≡CPh)₃ (III). According to the X-ray diffraction data, complexes II and III contain shortened Mn-Sn bonds (2.5178(5) and 2.5436(12) Å, respectively).     

Synthesis of tris(tetrathiafulvaleno)dodecadehydro- [18]annulenes and their self-assembly

[reaction: see text] Synthesis of electroactive tris(tetrathiafulvaleno)dodecadehydro[18]annulenes with ester substituents has been carried out with palladium-mediated cyclotrimerization of 4,5-diethynyl-TTFs. The TTF[18]annulenes produce stacked dimmers in solution and exhibit solvatochromism and thermochromism. The TTF[18]annulene-hexabutyl ester forms a molecular wire from an aqueous THF solution with cooperative S-S and pi-pi stacking interactions.     

Pentacarbonyl{tris[4‐(methylsulfonyl)phenyl]stannyl}manganese(I): an unexpected tetragonal structure

The title compound, [MnSn(C₇H₇O₂S)₃(CO)₅], is asymmetric but crystallizes in the highly symmetric tetragonal space group I. This is achieved without the need for any disorder, either around the Sn atom or in any of the methyl­sulfonyl groups. The environment around the Sn atom has the following geometry: Sn—Mn = 2.6564 (7) Å, mean Sn—C = 2.175 (5) Å, mean C—Sn—C = 103 (2)° and mean C—Sn—Mn = 115 (6)°. The crystal packing is assisted by weak Sn?O interactions between adjacent columns of mol­ecules, with the resulting geometry at Sn approaching highly distorted trigonal–bipyramidal.     

Poly[tris(diorganophosphinato)alanes]

Poly[tris(diorganophosphinato)alanes], [Al(OPRR′O)₃]_n, were synthesized in which the organic moieties (R,R′) contained from one to eighteen carbon atoms. Polymeric properties depended upon the organic moieties; polymers were fusible, tractable, and flexible when the organic moieties contained six or more carbon atoms. Soluble polymers were prepared by using mixtures of symmetrical and unsymmetrical phosphinates. One polymer, poly{bis[n-butyl(benzyl)phosphinato]di-n-octylphosphinatoalane}, exhibited a degree of polymerization greater than 1000 and an exceptionally high intrinsic viscosity of 37 dl/g. The properties of the different polymers are discussed, and feasible structures are proposed.     

Synthesis and structure of tetrakis(isopropylimino)bis-[tris(dimethylamino)silylamino]alane

A novel cage-type compound tetrakis(isopropylimino)bis[tris(dimethylamino)silylamino]alane, H₆Al₆(NⁱPr)₄[NSi(NMe₂)₃]₂, (1), was prepared by reaction of tris(dimethylamino)silylamine H₂NSi(NMe₂)₃ with poly(isopropyliminoalane) (HAlNⁱPr)₆. The molecular structure of 1 was determined and discussed on the basis of FTIR, NMR and X-ray crystallographic analysis.     

Synthesis and ESR spectra of [4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzosemiquinonato]thallium(i)

[4,6-Di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzosemiquinonato]thallium(i) was synthesized and characterized by IR and ESR spectroscopy. The hyperfine coupling constants with ^203/205Tl nuclei were found to depend strongly on the nature (solvating ability) of solvents. At 298 K, the HFC constant a _Tl changes from 3.09 mT in n-hexane up to 19.70 mT in tetramethylethylenediamine. The coordination number of solvation was found to be 1 for DMF—benzene and pyridine—hexane systems. The thermodynamic characteristics of solvation in the pyridine—hexane system were determined.     

Synthesis and characteristics of a nonaggregating tris(tetrathiafulvaleno)dodecadehydro[18]annulene

A new tris(tetrathiafulvaleno)dodecadehydro[18]annulene with six peripheral n-hexyl substituents was prepared by oxidative Glaser-Hay cyclization of a corresponding diethynylated tetrathiafulvalene (TTF) precursor. The electronic properties of the neutral and oxidized species were studied by both UV/Vis absorption spectroscopy and electrochemistry. From these studies, it transpires that the strongly violet-colored macrocycle does not aggregate in solution to any significant degree, which was confirmed by (1)H NMR spectroscopy. This reluctance towards aggregation contrasts that observed for related TTF-annulenes containing other peripheral substitutents. Oxidation of the TTF-annulene occurs in two three-electron steps as inferred from both the peak amplitudes and the spectroelectrochemical study. We find that the tris(TTF)-fused dehydro[18]annulene is more difficult to oxidize (by +0.20 V) than the silyl-protected diethynylated mono-TTF precursor. In contrast, the first vertical ionization energy calculated at the B3 LYP/6-311+G(2d,p) level for the parent tris(TTF)-fused dehydro[18]annulene devoid of peripheral hexyl substituents is in fact lower (by 0.44 eV). Moreover, the surface morphology of 1 d drop-cast on a mica substrate was investigated by atomic force microscopy (AFM). Crystalline domains with slightly different orientations were observed. The thickness of individual layers seen in the crystalline domains and the thickness of a monolayer obtained from a very dilute solution were determined to 1.8-1.9 nm. This thickness corresponds to the diameter of the macrocycle and the layers seen in the film are apparently formed when the molecules stack in the horizontal direction relative to the substrate.