A series of 2‐chloro‐1,3,2‐diazaphospholenes with different substitution patterns has been prepared from 1,4‐diazabutadienes according to a general synthetic methodology. Subsequent chloride abstraction with Lewis acids affords the corresponding 1,3,2‐diazaphospholenium salts. All products have been characterised spectroscopically and by single‐crystal X‐ray diffraction studies. A detailed analysis of trends in the structural parameters supports the interpretation that the unusual P–Cl bond lengthening in the diazaphospholenes is attributable to n(N)/σ*(P‐Cl) hyperconjugation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Reaction of 2-chloro-1,3,2-diazaarsolenes and -diazaphospholenes with Tl[Co(CO) 4 ] gives instable complexes of type [Co(ER 2 )(CO) 4 ] which decarbonylated to yield [Co(ER 2 )(CO) 3 ]. Spectroscopic and X-ray diffraction studies revealed that the tetracarbonyl complexes can be formulated as ion pair for E ϭ P and as covalent metalla-arsine for E ϭ As, and the tricarbonyl complexes as carbene-like species with a formal EϭCo double bond. A similar reactivity towards Tl[Co(CO) 4 ] was also inferred for 1,3,2diazastibolenes although the products were not isolable and their constitution remained uncertain. Evaluation of structural and com-1403 putational data suggests that the weak and polarized CoϪAs bond in [Co(AsR 2 )(CO) 4 ] can be characterized as an "inverse" MǞL donor-acceptor bond. The computational studies disclosed further η 2 (EN)-coordination of the EN 2 C 2 heterocycle as an alternative to the formation of a carbene-like structure for [Co(ER 2 )(CO) 3 ]. The η 2 -complex is less stable for E ϭ P but close in energy for E ϭ As and more stable than the carbene-like complex for E ϭ Sb.Scheme 2 (R ϭ tBu (1a, 3a, 4b), Mes (1b, 4b-9b)).

New N-heterocyclic stannylenes and germylenes were synthesized by transamination of E[N(SiMe3)2] (E = Ge, Sn) with alpha-amino-aldimines or ethylidene-1,2-diamines and were characterized by spectroscopic methods and in the case of the germylene 10 g by X-ray diffraction. The reactions of several germylenes and stannylenes with diazadienes were studied by using dynamic NMR and computational methods. Experimental and theoretical studies confirmed that metathesis with exchange of the Group 14 atom is feasible for both stannylenes and germylenes, with exchange rates being generally higher for stannylenes. The metathesis of the diazadiene 3 b and the stannylene 1 b follows second-order kinetics and exhibits a sizeable negative entropy of activation. The transfer reaction is inhibited by bulky substituents in both reactants and surprisingly coincides with a suppression of the fragmentation of the stannylene into tin and diazadiene. A connection between oxidative addition and ring fragmentation was also observed in the reaction of 1 f with sulfur. Density functional theory (DFT) calculations suggest that all metathesis reactions proceed via transient spirocyclic [1+4] cycloaddition products, the formation of which is generally endothermic and endergonic. The spirostannanes display a distorted Psi-tbp geometry at the tin atom and their cycloreversion requires low or nearly negligible activation energies; spirogermanes exhibit distorted tetrahedral central atoms and sizeable energy barriers with respect to the same reaction. Complementary studies of cycloadditions of diazadienes to triplet germylenes or stannylenes indicate that these reactions are exothermic. The lowest triplet state in the carbene homologues results from promotion of an electron from an n(N) orbital with pi character rather than the n(C)-sigma orbital as in carbenes, and singlet-triplet excitation energies decrease from carbon to tin. Spirostannanes exhibit a triplet ground-state multiplicity that implies that the energy hypersurfaces for the reactions of singlet and triplet stannylenes with diazadienes intersect; for germylenes, the singlet hypersurface is always lower in energy. A reaction mechanism explaining the different thermal stabilities of N-heterocyclic germylenes and stannylenes, and the coincidence between ring metathesis and thermal decomposition of the latter, is proposed based on the different separation of the singlet and triplet energy hypersurfaces.

Nanocomposite films and coatings with improved properties were produced from ultrasonic dispersed chitosan and hydrophilic bentonite nanoclay. Biohybrid coatings were applied onto argon-plasma-activated LDPE coated paper. The intercalation of chitosan in the silicate layers was confirmed by the decrease of diffraction angles as the chitosan/nanoclay ratio increased. Nanocomposite films and multilayer coatings had improved barrier properties against oxygen, water vapor, grease, and UVlight transmission. Oxygen transmission was significantly reduced under all humidity conditions. In dry conditions, over 99% reduction and at 80% relative humidity almost 75% reduction in oxygen transmission rates was obtained. Hydrophilic chitosan was lacking the capability of preventing water vapor transmission, thus total barrier effect of nanoclay containing films was not more than 15% as compared with pure chitosan. Because to very thin coatings ( 1 lm), nanoclay containing chitosan did not have antimicrobial activity against test strains. All coating raw materials were ''generally recognized as safe'' (GRAS) and the calculated total migration was in all cases 6 mg/dm 2 , thus the coatings met the requirements set by the packaging legislation. Processing of the developed bio-hybrid nanocomposite coated materials was safe as the amounts of released particles under rubbing conditions were comparable with the particle concentrations in a normal office environment.

Composite compounds based on hemp and flax fibers in triethyl citrate plasticized starch acetate were prepared by melt processing. For better properties and processability, compounds with plasticizer contents in the range 20–35 wt% were screened. Composites were prepared with fiber contents up to 50 wt%. The composite mechanical properties were measured from injection molded test specimens. A Young's modulus of 8.3 GPa and stress at maximum load of 51 MPa were obtained with 40 wt% flax fiber in a plasticized starch acetate with 20 wt% triethyl citrate. Decreasing the plasticizer and increasing the fiber content, the tensile properties were consistently improved. An almost linear relation between fiber content and the tensile properties was found. The increase of the fiber content first improved the impact strength, but at higher fiber contents resulted in a reduction of impact strength. The quality of the produced materials was found to be good; the variation in properties between duplicated compounds was acceptable low, the variation in density and fiber content along a single tensile specimen was low, and finally, the porosity content was low even at high fiber content. The latter result was verified with scanning electron microscope images of fracture surfaces of the composites. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers

This study is presented to predict the Young’s modulus of injection-molded short cellulosic fiber/plasticized starch acetate composites with variable fiber and plasticizer content. A modified rule of mixtures model is applied where the effect of porosity is included, and where the fiber weight fraction is used as the basic independent variable. The values of the input model parameters are derived from experimental studies of the configuration of the composites (volumetric composition, dimensions, and orientation of fibers), as well as the properties of the constituent fiber and matrix phases (density and Young’s modulus). The measured Young’s modulus of the composites varies in the range 1.1—8.3 GPa, and this is well predicted by the model calculations. A property diagram is presented to be used for the tailor-making of composites with Young’s modulus in the range 0.2—10 GPa.

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An extended family of heterometallic [(M1)2(M2)2(L-)4](n+) [2x2] grid-type arrays 1-9 has been prepared. The three-tiered synthetic route encompasses regioselective, redox and enantioselective features and is based on the stepwise construction of heteroditopic hydrazone ligands A-C. These ligands contain ionisable NH and nonionisable NMe hydrazone units, which allows the metal redox properties to be controlled according to the charge on the ligand binding pocket. The 2-pyrimidine (R) and 6-pyridine (R') substituents have a significant effect on complex geometry and influence both the electrochemical and magnetic behaviour of the system. 1H NMR spectroscopic studies show that the Fe(II) ions in the grid can be low spin, high spin or spin crossover depending on the steric effect of substituents R and R'. This steric effect has been manipulated to construct an unusual array possessing two low-spin and two spin-crossover Fe(II) centres (grid 8). Electrochemical studies were performed for the grid-type arrays 1-9 and their respective mononuclear precursor complexes 10-13. The grids function as electron reservoirs and display up to eight monoelectronic, reversible reduction steps. These processes generally occur in pairs and are assigned to ligand-based reductions and to the Co(III)/Co(II) redox couple. Individual metal ions in the heterometallic grid motif can be selectively addressed electrochemically (e.g., either the Co(III) or Fe(II) ions can be targeted in grids 2 and 5). The Fe(II) oxidation potential is governed by the charge on the ligand binding unit, rather than the spin state, thus permitting facile electrochemical discrimination between the two types of Fe(II) centre in 7 or in 8. Such multistable heterometallic [2x2] gridlike arrays are of great interest for future supramolecular devices incorporating multilevel redox activity.