Consecutive Transformations Research Articles

Reduced Uranium Complexes: Synthetic and DFT Study of the Role of π Ligation in the Stabilization of Uranium Species in a Formal Low-Valent State

Reaction of UCl(4)(THF)(4) with 1,3-[2,5-(i-Pr)(2)PhNC( horizontal lineCH(2))](2)C(6)H(4)Li(2) produced a complex formulated as [{1,3-[2,5-(i-Pr)(2)PhNC( horizontal lineCH(2))](2)C(6)H(4)}UCl(3)][Li(THF)(4)] (1) that exhibits a nonagostic interaction between one of the carbon atoms of the central phenyl ring and the U metal center. This interaction leads to significant weakening of the corresponding C-H bond, thereby facilitating proton removal in consecutive transformations. Attempts to form trivalent uranium derivatives were carried out by reacting the same ligand dianion with in situ-prepared "UCl(3)". The reaction indeed afforded a trivalent species formulated as {1,3-[2,5-(i-Pr)(2)PhNC( horizontal lineCH(2))](2)C(6)H(4)}U(mu-Cl)(3)[Li(THF)(2)](2) (2). The configuration of the ligand system in this complex is similar to that in 1, with the same type of arrangement of the central phenyl ring. Further reduction chemistry with a variety of reagents and conditions was examined. Reaction of 1 with 1 equiv of lithium naphthalenide at 0 degrees C did not afford 2 but instead gave a closely related U(III) complex formulated as {1,3-[2,5-(i-Pr)(2)PhNC( horizontal lineCH(2))](2)C(6)H(4)}U(THF)(mu-Cl)(2)[Li(Et(2)O)(2)] (3). Both of the trivalent complexes 2 and 3 reacted thermally in boiling THF, undergoing oxidation of the metal center to afford a new tetravalent compound {1,3-[2,5-(i-Pr)(2)PhNC( horizontal lineCH(2))](2)C(6)H(3)}U(THF)(mu-Cl)(2)[Li(THF)(2)] (4) in which the oxidation of the trivalent center occurred at the expense of the central phenyl ring C-H bond. Reaction of 1 with 3 equiv of lithium naphthalenide at room temperature afforded {{1,3-[2,5-(i-Pr)(2)PhNC( horizontal lineCH(2))](2)C(6)H(3)}U(mu-Cl)(mu-[O(CH(2))(3)CH(2)])[Li(DME)]}[Li(DME)(3)] (5). In this species, the tetravalent metal center forms a six-membered metallacycle ring with a moiety arising from THF ring opening. Reaction in DME afforded reductive cleavage of the solvent accompanied by reoxidation of U to the tetravalent state. Reduction of 1 in DME with 2 equiv of potassium naphthalenide at room temperature gave a mixture of two compounds having very similar structures. The two different species [{1,3-[2,5-(i-Pr)(2)PhNC( horizontal lineCH(2))](2)C(6)H(3)}UCl(OCH(3))][Li(DME)(3)] (6a) and [{1,3-[2,5-(i-Pr)(2)PhNC( horizontal lineCH(2))](2)C(6)H(3)}UCl(2)][Li(DME)(3)] (6b) cocrystallized in a ratio very close to 1:1 within the same unit cell. The methoxide group was generated from cleavage of the DME solvent. We also attempted the reduction of 1 with a different reducing agent such as NaH in DME. After a slow reaction, a new species formulated as {1,3-[2,5-(i-Pr)(2)PhNC( horizontal lineCH(2))](2)C(6)H(3)}U(mu-OCH(3))(3)(mu,eta(6)-Na)[eta(3)-Na(DME)] (7) was isolated in significant yield. Once again, the crystal structure revealed the presence of several methoxy groups coordinated to the U center in addition to the metalation of the ligand phenyl ring. To minimize solvent cleavage, reduction of 1 was also carried out at low temperature (-35 degrees C) and with a larger amount (4 equiv) of lithium naphthalenide. After suitable workup, the new species {[{1,3-[2,5-(i-Pr)(2)PhNC( horizontal lineCH(2))](2)C(6)H(3)}U{1,3-[2,5-(i-Pr)(2)PhN horizontal lineC(CH(3))](2)C(6)H(4)}][Li(DME)(THF)]}.Et(2)O (8) was isolated in significant yield. Even in this case, the uranium atom is surrounded by the expected trianionic, ring-metalated ligand. However, a second ligand unit surrounds the metal center, being bonded through a part of the pi system. Reaction of 1 with excess NaH in toluene proceeded slowly at room temperature, affording a significant yield of {[{1,3-[2,5-(i-Pr)(2)PhNC( horizontal lineCH(2))](2)C(6)H(3)}U{1,3-[2,5-(i-Pr)(2)PhN horizontal lineC(CH(3))](2)C(6)H(4)}{Na(DME)(2)}][Na(DME)(3)]}.(1)/(2)C(7)H(8) (9) after crystallization from DME/toluene. Similar to 8, the complex still contains one ring-metalated trianionic ligand and one intact ligand that has regained the H atoms and restored the two imine functions. Although according to their connectivities, complexes 8 and 9 could be assigned with the formal oxidation states +2 and +1, respectively, density functional theory calculations clearly indicated that these species contain additional spin density on the ligand system with the metal center in its more standard trivalent state.

Effect of Chemical Lithium Insertion into Rutile TiO2 Nanorods

Rutile TiO2 nanorods were synthesized by hydrolysis of TiCl4 followed by a hydrothermal method. Lithium insertion into the rutile nanorods was achieved by a chemical lithium insertion process. The structural evolution of nanostructured rutile upon lithium insertion was characterized by several experimental techniques, namely, XRD, TEM, SAED and 6Li MAS NMR. The XRD and TEM studies indicate the formation of lithium titanate phase (LixTiO2) during lithium insertion. Additionally, SAED patterns show that the lithium titanate phase has cubic symmetry. Finally, high magnetic field (21.1 T) 6Li MAS NMR reveals that the lithium titanate phase adopts two different structures depending on lithium content. Taken together, the four techniques consistently show that the insertion of lithium into rutile TiO2 nanorods causes two consecutive structural phase transformations to lithium titanate phases with spinel (Fd3m) and rocksalt (Fm3m) structures at x = 0.46 and 0.88, respectively. In addition, the broad line width...

Machine Learning Approach to Discovering Cascade Reaction Patterns. Application to Reaction Pathways Prediction

We propose a combinatorial learning procedure for discovering graph transformation patterns based on combining transformations that can be used in a consecutive fashion. Application of this kind of pattern to a specified chemical system allows to combine a sequence of consecutive transformations into a one-step operation limiting the complexity of a reaction tree. In a retrosynthetic sense, it provides a global strategy for bond disconnections to plan more efficient convergent syntheses. In a forward direction the approach reduces the number of iterations in order to exploring the courses of complex multistep processes. The procedure enhances the capabilities and applications of the CSB (Chemical Sense Builder) computer program to assist in organic synthesis, biochemistry, or medicinal chemistry. As an example, we present the automatic derivation of the transformation pattern for Ugi-type four-component reactions (reaction sequences) and its application to assist in the designing new cascade transformations for diversity-oriented synthesis (DOS).

Mechanism of ammonia oxidation over PGM (Pt, Pd, Rh) wires by temporal analysis of products and density functional theory

The mechanism of ammonia oxidation over Pt, Pd, and Rh wires has been investigated in the Temporal Analysis of Products (TAP) reactor at relevant temperatures in industrial ammonia burners. The results of primary ( NH 3 + O 2 ) and secondary ( NH 3 + NO ) interactions with isotopically labeled ammonia at 1073 K enable to conclude that the overall reaction pathways to NO, N 2O, and N 2 are equivalent on the three noble metals. NO is a primary reaction product, while N 2 and N 2O originate from consecutive NO transformations. The extent of the secondary reactions determines the net NO selectivity. Rhodium is the most active catalyst for the unwanted reduction of NO by NH 3, while platinum shows the lowest activity. This explains the superior NO selectivity attained over Pt and, therefore, its industrial application. The TAP-derived selectivity ranking was substantiated by Density Functional Theory calculations on the (100) facets of the noble metals. We proved experimentally that NO selectivity approaching 100% at complete NH 3 conversion can be equivalently attained over Pt, Pd, and Rh by increasing the oxygen content in the feed. For a feed of O 2 / NH 3 = 10 , both N 2O and N 2 production are suppressed due to the impeded NO dissociation and favored NO desorption at high oxygen coverage.

Consecutive multi-component syntheses of heterocycles via palladium-copper catalyzed generation of alkynones

Alkynones are prominent three-carbon building blocks in heterocyclic chemistry. They can be generated very easily and efficiently by modified Sonogashira coupling of acid chlorides and terminal alkynes. Mild reaction conditions now set the stage for new diversity-oriented routes to heterocycles by sequential and consecutive transformations. Hence, isoxazoles, indolizines, pyrazoles, pyridimines, 1,5-benzoheteroazepines, furans, oxazoles, and tetrahydro-β-carbolines are accessible by consecutive coupling-cycloaddition or coupling-addition-cyclocondensation multi-component sequences.

Phase transformations of a spray-dried iron catalyst for slurry Fischer–Tropsch synthesis during activation and reaction

The consecutive phase transformations of a precipitated spray-dried iron-based catalyst for slurry Fischer–Tropsch synthesis (FTS) during activation and reaction process were investigated using Mössbauer effect spectroscopy (MES). It was found that the fresh iron catalyst activation in situ using syngas resulted in the formation of a mixture of iron carbides and superparamagnetic (spm) phases. The relatively small size of fresh iron crystallites was an important factor in the formation of ε′-Fe 2.2C. During the reduction process, Fe 3+ (spm) phase was easier to be reduced than α-Fe 2O 3 phase. Fe 3O 4 was not an active phase for FTS. The transformation of α-Fe 2O 3 into Fe 3O 4 before carbides formation was necessary to obtain FTS activity of the iron catalyst. There was a correlation between the content of CH 4 in tail gas and the amount of iron carbides during activation. It was found that carbonization was the dominating phase transformation when the FTS reaction temperature increased from 250 °C to 270 °C. However, the oxidization was more remarkably at higher FTS reaction temperature. χ-Fe 5C 2 was the main iron phase at lower reaction temperature. The changes in the bulk compositions resulted in the variation in catalyst activity during FTS. The results of this study showed that the active phase for FTS was a mixture of carbides and corresponding amounts of superparamagnetic phase.

Diastereo‐ and Enantiomerically Pure Allylboronates: Their Synthesis and Scope

Allylboronates are highly attractive reagents for allyl additions. Enantiomerically pure, stable reagents with a stereogenic centre in alpha-position to boron are especially versatile, albeit often difficult to synthesize. Starting from boron-containing allyl alcohols 6 and 7, which are discussed in detail herein, a set of reagents were obtained via [3,3]-sigmatropic rearrangements and consecutive transformations in the side chain. The configurations could be established first by chemical correlation, but also by X-ray crystallography (16, 18, 34, and 39). Allyl additions were performed resulting in the formation of predominantly (Z)-configured homoallylic alcohols (31, 43-45) with high enantiomeric excess. Detailed investigations on the matched-mismatched interaction between the reagents 15/16 (and ent-15/ent-16, respectively) and isopropylidene glyceraldehyde 42d are presented.

Asymmetric Reductive Acylation of Aromatic Ketoximes by Enzyme-Metal Cocatalysis

We have developed an efficient procedure for the asymmetric synthesis of chiral amides from ketoximes. This one-pot procedure employs two different types of catalysts, Pd nanocatalyst and lipase, for three consecutive transformations including hydrogenation, racemization, and acylation. Eight ketoximes have been efficiently transformed to the corresponding amides in good yields (83-92%) and high enantiomeric excesses (93-98%).

Synthesis of [4.6.4.6]Fenestradienes and [4.6.4.6]Fenestrenes Based on an 8π−6π-Cyclization-Oxidation Cascade

Fenestranes are regarded as a particularly challenging synthetic targets, and only few syntheses have been reported in the recent past. These rare compounds of synthetic and theoretical interest are a class of tetracyclic skeletons, defined as doubly a,a'-bridged spiroalkanes. The reported results are focused on the synthesis of new and original [4.6.4.6]fenestradienes 3a-f and [4.6.4.6]fenestrenes 4a-e. Our approach implies the formation of this tetracyclic structure by a reaction cascade, based on consecutive transformations starting from the trienyne 1a-f: an initial soft hydrogenation using a P-2 Nickel catalyst at room temperature, followed by a conrotatory 8p electrocyclization and a disrotatory 6p electrocyclization and a final oxidation. Several examples of this type of new compounds are described in this Communication.

A mechanistic study of TiO2 anatase-to-rutile phase transformation under mechanical processing conditions

Abstract A systematic investigation on the mechanistic features of the anatase-to-rutile phase transformation under mechanical treatment conditions has been performed. Mechanical processing was carried out first on pure anatase powders and was demonstrated to induce two consecutive transformations from anatase to TiO 2 II and from this to rutile. Phase transformation kinetics was described by means of kinetic curves and the rate quantified by two rate constants. The mechanical treatment was successively performed on anatase–rutile powder mixtures with different rutile contents. Being the final product of phase transformations, rutile acts here as an inert phase. Its effect on rate constants was carefully ascertained and used to further point out their physical meaning.

RETRACTED: Novel synthetic approach to 1α,25-dihydroxyvitamin D3 and analogues

A mild and stereoconvergent synthesis of 1alpha,25-dihydroxyvitamin D(3) (calcitriol, 1a) is described. The key step is a cascade process consisting of two consecutive transformations: An initial palladium-catalyzed 6-exo-cyclocarbopalladation of vinyl triflate 4 followed by a Negishi cross-coupling reaction with alkenyl zinc 3. This approach is of interest for the rapid synthesis of a variety of new vitamin D(3) analogues of therapeutic potential, especially those modified at the triene and ring-A. The mildness of the method also allows the preparation of thermal sensitive vitamin D(3) analogues.

Photochemistry of 2-Alkoxymethyl-5-methylphenacyl Chloride and Benzoate

Irradiation of 2-(alkoxymethyl)-5-methyl-alpha-chloroacetophenones (1a-c) and 2-(methoxymethyl)-5-methylphenacyl benzoate (1d) in dry, nonnucleophilic solvents afforded 3-alkoxy-6-methylindan-1-ones (3a-c) in very high chemical yields. 3-Methylisobenzofuran-1(3H)-one (2) was, however, isolated as a major photoproduct in the presence of trace amounts of water. Quenching experiments and laser flash spectroscopy revealed that the indanone derivatives 3 are formed by 1,5-hydrogen migration from the lowest triplet excited state of the acetophenones 1 and cyclization of the resulting photoenols. In contrast, production of the lactone 2 in wet solvents was found to result from two consecutive photochemical transformations. The photoenols produced by photolysis of 1a-c add water as a nucleophile to form 2-acetyl-4-methylbenzaldehyde (4), which is further converted to 2 via a second, singlet state photoenolization process. Exhaustive photolysis of 1a in methanol produced the acetal 2-(dimethoxymethyl)-5-methylacetophenone (7a) as the exclusive product. The remarkable selectivity of these photoreactions may well be useful in synthetic organic chemistry.

Free radicals as intermediates in catalytic oxidation of light alkanes: new opportunities

The analysis of catalytic partial oxidation of light alkanes indicates that processes involving this group proceed via the formation and consecutive transformations of free radicals. Depending on the properties of the catalytic system and reaction conditions the same primary radical can give different final products, olefins, oxygenated organic substances and carbon oxides. An approach to design a complex catalytic system for efficient alkane partial oxidation based on separation of zones where free radicals are formed and where they are transformed into desired products is suggested and examples of its implementation are presented.

Pd-Catalyzed Carbocyclization−Negishi Cross-Coupling Cascade: A Novel Approach to 1α,25-Dihydroxyvitamin D3 and Analogues

[reaction: see text] A mild palladium-catalyzed cascade has been used for the synthesis of the hormone 1alpha,25-dihydroxyvitamin D3 (calcitriol, 1a) and its analogues 1b and 1c. This one-pot process involves two consecutive transformations at room temperature: An initial palladium-catalyzed 6-exo-cyclocarbopalladation of vinyl triflates followed by a Negishi cross-coupling reaction with an alkenyl zinc. This novel strategy opens new possibilities for the preparation of a variety of new vitamin D analogues of therapeutic potential, particularly with modifications at the triene and/or ring-A.

Lax pair for strings in Lunin-Maldacena background

Recently Lunin and Maldacena used an SL(3,R) transformation of the AdS_5 x S^5 background to generate a supergravity solution dual to a so-called beta-deformation of N = 4 super Yang-Mills theory. We use a T-duality-shift-T-duality (TsT) transformation to obtain the beta-deformed background for real beta, and show that solutions of string theory equations of motion in this background are in one-to-one correspondence with those in AdS_5 x S^5 with twisted boundary conditions imposed on the U(1) isometry fields. We then apply the TsT transformation to derive a local and periodic Lax pair for the bosonic part of string theory in the beta-deformed background. We also perform a chain of three consecutive TsT transformations to generate a three-parameter deformation of AdS_5 x S^5. The three-parameter background is dual to a nonsupersymmetric marginal deformation of N=4 SYM. Finally, we combine the TsT transformations with SL(2,R) ones to obtain a 6+2 parameter deformation of AdS_5 x S^5.

Grain Structure of Fe-0.3mass%C-9mass%Ni Steel Processed through .ALPHA..RAR..GAMMA..RAR..ALPHA.' Transformation Caused by Spontaneous Reverse Transformation

α→γ→α' (ferrite→austenite→martensite) transformation caused by spontaneous reverse transformation (SRT) in Fe-0.3C-9Ni mass% steel has been demonstrated using laboratory rolling mill, and grain structure of the plate has been investigated. SRT is a new process to obtain an ultra refined austenite, and resulting ultra refined transformation products, which occurs due to adiabatic heating caused by deformation at temperatures in ferrite phase field. SRT occurred all through the plate thickness by intensive rolling with 90% reduction and final microstructure was ultra-refined martensite. Mean lineal intercepts of the martensite grains were 0.90 μm at mid thickness and 0.83 μm at quarter thickness. Ultra-refined grain structure attributes to enhancement of austenite nucleation due to the intensive rolling before α→γ→α' transformation. The martensite texture after the α→γ→α' transformation caused by SRT composed of RD//‹110›α and ND//‹111›α fibers. However, these were not sharp, thus crystallographic grain orientation was quite randomised in spite of the intensive rolling. Two consecutive transformations weakened the initial ferrite rolling texture remarkably. Randomization of the grain orientation was more prominent at the quarter-thickness than at the mid-thickness due to a shear strain.

On invariant tori of full dimension for 1D periodic NLS

Consider the NLS with periodic boundary conditions in 1D (0.1)iut+Δu+Mu±ɛu|u|4=0, where M is a random Fourier multiplier defined by (0.2)Mu^(n)=Vnu^(n) and (Vn)n∈Z are independently chosen in [-1,1]. The quintic nonlinearity in (0.1) is unimportant and may be replaced by u|u|p-2,p∈2Z,p⩾4. We give a proof of the following fact. Theorem. For appropriate M, (0.1) has an invariant tori T (of full dimension) satisfying 12e-r|n|<|qn|<2e-r|n|(n∈Z,q∈T) (r>0 is arbitrary). Remark. The statement holds in fact for most (Vn)n∈Z∈[-1,1]Z, although not explicitly proven here. Written in Fourier modes (qn)n∈Z, the Hamiltonian corresponding to (0.1) is given by (0.3)H(q,q¯)=∑(n2+Vn)|qn|2+ɛ∑n1-n2+n3-n4+n5-n6=0qn1q¯n2qn3q¯n4qn5q¯n6. The proof of Theorem 1 will proceed along the ‘usual’ KAM scheme where the perturbation is eventually removed by consecutive canonical transformations of phase space. The most relevant literature in the present context of an infinite dimensional phase space are the papers of Frohlich et al. [Frohlich, Spencer, Wayne, Localization in disordered, nonlinear dynamical systems, J. Statist. Phys. 42 (1986) 247–274] and especially Poschel [Poschel, Small divisors with spatial structure in infinite dimensional Hamiltonian systems, CMP 127 (1990) 351–393] on disordered systems. Both [Frohlich, Spencer, Wayne, Localization in disordered, nonlinear dynamical systems, J. Statist. Phys. 42 (1986) 247–274, Poschel, Small divisors with spatial structure in infinite dimensional Hamiltonian systems, CMP 127 (1990) 351–393] consider Hamiltonians with short-range interactions and hence these results do not apply to our problem. It turns out, however that the scheme, as elaborated on in great detail in [Poschel, Small divisors with spatial structure in infinite dimensional Hamiltonian systems, CMP 127 (1990) 351–393], is still applicable to (0.3), due to special arithmetical features as will be explained in the next section. Roughly speaking, the key point is the following observation. Let (ni) be a finite set of modes, |n1|⩾|n2|⩾⋯ and (0.4)n1-n2+n3-⋯=0. In the case of a ‘near’ resonance, there is also a relation (0.5)n12-n22+n32-⋯=o(1). Unless n1=n2, one may then control |n1|+|n2| from (0.4), (0.5) by ∑j⩾3|nj|. This feature is specifically 1-dimensional and we do not know at this time how to prove a 2D-analogue of Theorem 1, considering for instance the cubic NLS iut+Δu±u|u|2=0 on T2. It should also be pointed out that almost periodic solutions on a full set of frequencies for NLS and NLW in 1D were constructed in earlier works (see [Bourgain, Construction of approximative and almost periodic solutions of perturbed linear Schrodinger and wave equations, GAFA 6 (2) (1996) 201–230] and [Poschel, On the construction of almost periodic solutions for nonlinear Schrodinger equations, Ergodic Theory Dynamical Systems 22 (5) (2002) 1537–1559]). These invariant tori (of full dimension) were obtained by successive small perturbations of finite-dimensional tori, resulting in very strong compactness properties and in fact a nonexplicit decay rate of the action variables In for n→∞. On the other hand, the construction in this paper (similarly to [Poschel, Small divisors with spatial structure in infinite dimensional Hamiltonian systems, CMP 127 (1990) 351–393]) treats all Fourier modes at once and requires explicit and realistic decay conditions. The multiplier M=(Vn) in (0.3) is to be considered as a parameter and (0.1) a parameter-dependent equation. The role of this parameter is essential to ensure appropriate nonresonance properties of the (modulated) frequencies along the iteration. In the absence of exterior parameters, these conditions need to be realized from amplitude–frequency modulation and suitable restriction of the action-variables. This problem is harder. Indeed, a fast decay of the action-variables (enhancing convergence of the process) allows less frequency modulation and worse small divisors (cf. [Bourgain, On diffusion in high-dimensional Hamiltonian systems and PDE, J. Anal. Math. 80 (2000) 1–35]).

Cover Picture: Palladium‐Catalyzed Enantioselective Domino Reaction for the Efficient Synthesis of Vitamin E (Angew. Chem. Int. Ed. 2/2005)

A domino reaction consists of several consecutive transformations in which the functions required for one reaction are generated in the preceding bond‐formation or fragmentation step. L. F. Tietze et al. applied this concept to the synthesis of vitamin E described on page 257 ff. They developed an enantioselective palladium‐catalyzed process for the construction of the chiral chroman framework with 96 % ee and concomitant introduction of part of the side chain.

Mechanism of novel consecutive rearrangements of cyclobutene-fused diphenylhomobenzoquinones catalyzed by lewis acids.

Lewis acid catalyzed rearrangements of highly strained [2 + 2] photoadducts 1a-d of diphenylhomobenzoquinone with various acetylenes were investigated under the influence of AlCl(3), SnCl(4), BF(3), and TiCl(4). With the relief of steric strain, these tricyclo[5.2.0.0(3,5)]non-8-ene-2,6-diones underwent the three steps of consecutive skeletal transformations. The first step was the two-way cyclobutene ring-cleavage reaction with a Wagner-Meerwein vinyl migration to either Lewis acid activated carbonyl function. This process virtually occurred under the anchimeric assistance of the endo-phenyl ring to give, after proton transfer, the phenylene-bridged tetracyclic keto alcohols 2 and 3, respectively. The next step was the acid-induced cyclopropane ring cleavage of only 3 to lead to bicyclic diones 4 via a following stereoselective proton transfer. The last one involved a Michael-type intramolecular cyclization of 4 accompanied by a proton transfer to afford thermodynamically less stable tricyclic diones 5alpha which epimerized to 5beta only by TiCl(4). The factors that control the selectivity and the reactivity of these tandem reactions were addressed on the basis of the X-ray crystal analyses as well as the PM3 calculations. It was found the present Lewis acid-catalyzed rearrangements were very dependent on the substituents of 1a-d and the nature of the Lewis acids.

Synthesis, Structure, and Properties of New Hybrid Nanocomposites Containing the [Mo6( 3-Cl)8]4+Cluster

A new type of hybrid nanocomposite material is produced via consecutive outer-sphere transformations of a Mo-containing cluster. Cluster monomers with the general formula (Bu4N)2[(Mo6Cl8)(CF3COO)6 – n CH2=CHCOO n ] (n= 1–3) are synthesized and characterized for the first time. The bulk radical copolymerization of such monomers with acrylic acid is an interfacial process and leads to the formation of hybrid (metal-containing polymeric) nanocomposites. The synthesized copolymers (≃1–5 wt % Mo, M η ≃ 270000, 5–24 cluster units per polymer chain) are examined by nuclear magnetic resonance and IR spectroscopy. The results indicate that the copolymers contain stereoregular (syndiotactic) polyacrylic acid. The structure of the cluster-containing composites, the distribution of cluster units over the polymer chain, and the origin of stereoregularity in such systems are discussed. According to differential thermal analysis results, the introduction of clusters into the polymer chain has an insignificant effect on the thermal stability of the nanocomposites. The same is evidenced by the results on the molecular–topological properties of the nanocomposites.