Table of contents

Published data on the synthesis and chemical properties of complexes of Group 4–10 transition metals (d elements) with η ⁶-tetramethylfulvene and η⁷-trimethylallyldiene ligands, formed from the pentamethylcyclopentadienyl complexes of these metals, are described systematically. A description of the structures of these complexes in terms of a "specific" resonance hybrid of fulvene and methylenecyclopentadienyl (or allyldiene and dimethylenecyclopentadienyl) structures is proposed. It is noted that similar properties or behaviours of the fulvene and allyldiene complexes can be followed both for compounds formed by metals of the same Group and for compounds of elements of the same transition row with identical electron configurations.

Data on substitution reactions at boron atoms in 10–12-vertex metallacarboranes, which are of fundamental and applied significance, are generalised. The possible mechanisms of substitution reactions and the influence of the metal fragment on substitution positions in the polyhedron are discussed.

The state-of-the-art in the structural investigations into fullerene derivatives is surveyed. The crystal structures of individual fullerenes and of their derivatives determined experimentally by single-crystal X-ray diffraction are systematised. The results of powder X-ray diffraction and EXAFS spectroscopy are overviewed for those classes of derivatives that have been insufficiently studied by single-crystal X-ray diffraction. Patterns of packing of the fullerene spheres encountered in crystal structures are described and representative examples of the most typical motifs are given. Reasons for the rotational disorder, which often hampers structure determination for fullerene derivatives, and its classification are considered. A model of the "rubber cavity" is introduced, which allows prediction of typical mutual orientations of disordered molecules. The redistribution of bond lengths upon σ- and π-functionalisation of the carbon core is analysed based on the information retrieved from the Cambridge Structural Database. Factors affecting the molecular packing density in crystalline derivatives of fullerenes are discussed in relation to the quality of the diffraction data attainable for them.

New trends in the development of polycondensation methods, elucidation of the main principles of macromolecular design of polymeric chains and preparation of novel promising condensation polymers are considered and analysed.

The review concerns the syntheses of polymeric nanocomposites containing encapsulated nanoparticles formed in nanostructured polymeric systems including block copolymers, dendrimers, nanoporous polymers, polyelectrolyte gel–surfactant complexes and multilayered films. Nanostructures in amphiphilic block copolymers can form spontaneously both in the bulk (block microsegregation) and in solution (block copolymer micelle). In polymeric systems, nanostructures play the role of nanoreactors for the growing nanoparticles. The nanoparticle size, shape and size distribution are controlled by the nanostructure characteristics and synthesis conditions. The catalytic, magnetic and optical properties of these nanostructured polymeric nanocomposites are discussed.