Das Indiumsesquichlorid,In2Cl3: ein pseudobinäres,gemischtvalentes Indium(I)-hexachloroindat(III)

Indium Sesquichloride, In₂Cl₃: a Pseudobinary, Mixed-valence Indium(I) Hexachloroindate(III) Colorless In₂Cl₃, obtained by reduction of InCl₃ with metallic In, according to In[In^IIICl₆] a pseudobinary, mixed-valence indium(I) hexachloroindate(III), crystallizes orthorhombic (Pnma, Z = 32) with a = 1261.4(3), b = 2523.8(5), c = 1456.2(2) pm (Guinier-Simon data), V_m(In₂Cl₃) = 87.3 cm³ × mol^?1. In^III occupies octahedral holes separated from each other (d?(In^III? Cl) = 251 pm). Coordination numbers of 7 to 11 are observed for In^I (d?(In^I? Cl) = 329–359 pm). In₂Cl₃ is isotypic with α-Tl₂Cl₃.     

Reaction of Tetracopper(I)-Phosphonitocavitand with PhSeSiMe3: Synthesis and Structure of a Polyanionic Cluster [pyH]6[(CuCl)9(μ3-SePh)5(μ4-SePh)]

Treatment of tetracopper(I)-phosphonitocavitand [1·Cu₄(μ-Cl)₄(μ₄-Cl)] (2) (1 = tetraphosphonitocavitand [rccc-2,8,14,20-tetrakis-(iso-butyl)-phosphonitocavitand (C₄₄H₄₈O₈P₄Ph₄)]) with PhSeSiMe₃ in THF at low temperature afforded a novel polyanionic cluster [pyH]₆[(CuCl)₉(μ₃-SePh)₅(μ₄-SePh)] (4) as a major product along with a new tetracopper(I)-phosphonitocavitand (3) with a centered μ₃-Cl. Molecular structure of anionic cluster in 4 consists of six PhSe⁻ bridging ligands containing five μ₃-SePh and one exceptional μ₄-SePh bridging nine copper atoms, of which eight copper atoms have trigonal coordination geometry and the other has distorted tetrahedral geometry. Dedicated to Professor Han-Qin Liu on the occasion of his 70th birthday.     

Reactivity ratios of styrene and methyl methacrylate at 90°C

From the conversion–composition data of Gruber and Elias, the reactivity ratios of styrene (M₁) and methyl methacrylate (M₂) were calculated to be r₁ = 0.55 ± 0.02 and r₂ = 0.58 ± 0.06 at 90°C. The least-squares method was then used on these and literature values at other temperatures to obtain the Arrhenius expressions: In r₁ = 0.04736 – (235.45/T), and ln r₂ = 0.1183 – (285.36/T). Using literature values for the homopolymerization steps, A₁₁ = 2.2 × 10⁷l./mole-sec., E₁₁ = 7.8 kcal./mole, and A₂₂ = 0.51 × 10⁷ l./mole-sec.^?1, E₂₂ = 6.3 kcal./mole, activation energies and frequency factors were then calculated for the cross-polymerization steps: A₁₂ = 2.1 × 10⁷ l./mole-sec., E₁₂ = 7.3 kcal./mole, and A₂₁ = 0.45 × 10⁷ l./mole-sec., E₂₁ = 5.7 kcal./mole.     

X‐Ray Single Crystal Refinement and Superconductivity of La3Ni2B2N3

Crystalline samples of La₃Ni₂B₂N₃ were synthesized using solid state metathesis reactions from combinations of La, LaCl₃, NiCl₂ together with Li₃BN₂. The structure was determined by single crystal X‐ray diffraction (I4/mmm (No. 139), a = 372.95(2) pm, c = 2056.3(2) pm, R₁ = 0.027, wR₂ = 0.062) and confirmed earlier results from neutron powder diffraction. La₃Ni₂B₂N₃ contains BN units capping square planar Ni layers. Isolated nitrogen atoms reside in La₆ octahedra. Magnetic measurements on several bulk samples exhibit superconductivity at temperatures below 14.6 K.     

Cyclische Kieselsäurederivate

Cyclic Silicic Acid Derivatives By reaction of SiCl₄ with oxygen at elevated temperatures a number of chlorsiloxanes consisting of more or less fused rings can be prepared of which those components of low molecular weight can be separated by combining distillation and crystallization. Methyl and ethyl esters of silicic acids are obtained by reaction with methyl or ethyl nitrite, resp. The compounds are characterized by silicon n.m.r. and mass spectroscopy.     

Metalations—XVI : Polylithiation at benzylic positions

Metalation of mesitylene with butyllithium in hexane in the presence of tetramethylethylenediamine yields mono-, di- and trilithiated benzylic compounds (1–5), characterized as their silylated derivatives. Dilithiation occurred partly at the same but preferentially at different methyls. The symmetrical tris-1,3,5-(lithiomethylene)benzene was the main product. Similar metalation occurred with m-xylene. o-Xylene gave also dilithiated products, but at a slower rate, and p-xylene gave slowly and exclusively the gem-dilithio-derivative.The results were explained by greater stabilization of polylithio derivatives with charges all on the starred carbons of the conjugated system, rather than those with charges uniformly dispersed on all carbons. CNDO/2 calculations of the energy of the anions account only partially for the order of stability of most of the studied compounds, but a good correlation between this experimental order and the energies of the lithium compounds was found.     

Biomimetic cycloaddition approach to tropolone natural products via a tropolone ortho-quinone methide

[reaction: see text] A study toward a possible biomimetic hetero Diels-Alder reaction is reported between humulene and a novel tropolone ortho-quinone methide. A suitable tropolone ortho-quinone methide precursor has been prepared from 3-methyl-2-furoate. Heating the ortho-quinone methide precursor gave a tropolone ortho-quinone methide, which in the presence of humulene underwent a hetero Diels-Alder reaction to give a deoxy analogue of epolone B.     

Evidence for facile atropisomerism and simple (non-nucleophilic) biradical-forming cycloaromatization within kedarcidin chromophore aglycon

The kinetics and thermodynamics of atropisomerism within the protected kedarcidin chromophore aglycon 8, as well as a series of ansa-bridged synthetic intermediates leading to 8, were determined by 1H NMR spectroscopy. The data show that the ratio of atropisomeric forms of chloropyridine-bridged ansa intermediates is subject to wide variation with seemingly subtle structural variation. The vinyl bromide 4, for example, in the first X-ray structure determination of a kedarcidin ansa-bridged system, was found to exist as a single atropisomer in the solid state, but a nearly equal mixture (K = 0.70) of isomers in solution (t1/2 for isomer interconversion approximately 0.2 s at 20 degrees C). The aglycon 8, a 2.2:1 mixture of atropisomers, was found to undergo direct unimolecular biradical-forming cycloaromatization at ambient temperature in a mixture of 1,4-cyclohexadiene-benzene, without nucleophilic activation. The product 9 was formed as a single atropisomer (k = 2 x 10-4 s-1, t1/2 = 58 min, 81% yield), suggesting that the rate of atropisomerism within 8 is rapid with respect to cycloaromatization. The rate of cycloaromatization of 8 was found to be highly solvent-dependent, being more rapid in the presence of a good hydrogen-atom donor, consistent with the earlier model studies of Hirama et al. that showed that certain nine-membered cyclic (Z)-enediynes may equilibrate with their biradical cycloaromatization products. Incubation of 8 with beta-mercaptoethanol, under conditions mimicking experiments leading to DNA cleavage with kedarcidin, showed no evidence for nucleophilic activation. The product of direct cycloaromatization (9) was isolated instead. The evidence suggests that kedarcidin, like the enediyne agent C-1027, is capable of spontaneous thermal biradical formation without prior chemical activation.     

Studies directed toward the total synthesis of discodermolide: asymmetric synthesis of the C1-C14 fragment

[structure: see text] A convergent and stereoselective assembly of the C1-C14 subunit of marine natural product (+)-discodermolide has been completed. The approach employs chiral allylsilane bond construction methodology to establish four of the eight stereogenic centers. Key fragment coupling is achieved via an efficient stereoselective acetate aldol reaction between C1-C6 and C7-C14 subunits.