Formation of two isomeric closo-[(eta5-C5H5)FePC2B8H10] phosphadicarbaborane analogues of ferrocene via isolable eta1-bonded complexes of the [7-[(eta5-C5H5)Fe(CO)2]-(eta1-nido-PC2B8H10)] type

The reaction of nido-[7,8,9-PC(2)B(8)H(11)] (1) with [[CpFe(CO)(2)](2)] (Cp=eta(5)-C(5)H(5) (-)) in benzene (reflux, 3 days) gave an eta(1)-bonded complex [7-Fp-(eta(1)-nido-7,8,9,-PC(2)B(8)H(10))] (2; Fp=CpFe(CO)(2); yield 38 %). A similar reaction at elevated temperatures (xylene, reflux 24 h) gave the isomeric complex [7-Fp-(eta(1)-nido-7,9,10-PC(2)B(8)H(10))] (3; yield 28 %) together with the fully sandwiched complexes [1-Cp-closo-1,2,4,5-FePC(2)B(8)H(10)] 4 a (yield 30%) and [1-Cp-closo-1,2,4,8-FePC(2)B(8)H(10)] 4 b (yield 5%). Compounds 2 and 3 are isolable intermediates along the full eta(5)-complexation pathway of the phosphadicarbaborane cage; their heating (xylene, reflux, 24 h) leads finally to the isolation of compounds 4 a (yields 46 and 52%, respectively) and 4 b (yields 4 and 5%, respectively). Moreover, compound 3 is isolated as a side product from the heating of 2 (yield 10%). The structure of compound 4 a was determined by an X-ray structural analysis and the constitution of all compounds is consistent with the results of mass spectrometry and IR spectroscopy. Multinuclear ((1)H, (11)B, (31)P, and (13)C), two-dimensional [(11)B-(11)B]-COSY, and (1)H[(11)B(selective)] magnetic resonance measurements led to complete assignments of all resonances and are in excellent agreement with the structures proposed.     

Synthesis of Highly Functionalized Fluorinated Porphyrins

Highly functionalized fluorinated porphyrins were synthesized by a convergent strategy. Nucleophilic substitution using fluorinated branched unit and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin afforded highly functionalized fluorinated porphyrin 8 containing 24 fluorinated chains in the peripheral region.     

Thermal analysis of polyaniline poly(N-vinylpyrrolidone)-stabilized dispersions

The polyaniline dispersions stabilized with poly(N-vinylpyrrolidone) (PANI/PVP) were synthesized by oxidative polymerization with different mass ratios of PANI and PVP and different molar concentrations of the components in the polymerization mixture. The composite powders prepared from colloidal PANI/PVP dispersions were characterized by thermogravimetry and differential thermal analysis. The change in the ratio of PANI and PVP as well as the starting molar concentrations of aniline hydrochloride and oxidant has influence on the resulting properties of the dispersions. Concerning the doping, the results show that PANI/PVP powders are stable up to approximately 160 °C. Degradation of polymer chains starts at temperatures above 250 °C. The PANI/PVP composite powders with lower content of PANI exhibit slightly higher thermal stability. Further, colloidal PANI/PVP dispersions were screen-printed on aluminum foil for infrared spectroscopic characterization and on poly(ethylene terephthalate) foil for electrical measurements. The sheet resistance of printed layers measured by two-point probe was of the order of tens to thousands of kΩ sq^?1. The influence of both the change in the composition and the drying temperature is discussed.     

Improved synthesis of arachno-6,9-C2B8H14 and its halogenation under electrophilic conditions

A convenient synthesis of arachno-6,9-C₂B₈H₁₄, based on the reduction of nido-5,6-C₂B₈H₁₂ with sodium tetrahydroborate, is reported. Electrophilic halogenation of the former carborane produced a series of 1-X-6,9-C₂B₈H₁₃ (X = Cl, Br and I) derivatives whose constitution was established on the basis of their ¹H and ¹¹B NMR spectra.     

Synthetic routes to linear oligo-Tröger's bases

Derivatives of Tr?ger's base (TB) have played important roles in receptor construction due to their rigid V-shape. A new class of these compounds are the oligo-TBs, which can function as cavitands. Herein, we describe both stepwise and one-step (oligomerization) methods suitable for the preparation of linear oligo-TBs.     

Enantioseparations of non-benzenoid and oligo-Tröger’s bases by HPLC on Whelk O1 column

The separation of enantiomers of several ‘bis- and tris-Tröger’s bases’ by HPLC on commercially available chiral stationary phase Whelk O1 is described for the first time. The observed structure–enantioselectivity relationships are in agreement with the previously established molecular recognition model. For all ‘bis- and tris-Tröger’s bases’ studied, satisfactory to excellent enantioselectivities were observed.