Rare-earth amidate complexes. Easily accessed initiators for epsilon-caprolactone ring-opening polymerization

The direct synthesis of yttrium amidate complexes using the simple reaction of amide proligands and Y(N(SiMe3)2)3 results in the high-yielding preparation and isolation of crystalline, monomeric materials. The complex, tris(N-2',6'-diisopropylphenyl(naphthyl)amidate)yttrium mono(tetrahydrofuran) (4), was structurally determined to be a 7-coordinate C1 symmetric structure, maintaining one bound tetrahydrofuran molecule. Compound 4 (C12H17[NCO]C10H7)3Y(C4H8O) crystallized in the monoclinic space group P2(1)/c with a = 13.7820(11) A, b = 33.598(3) A, c = 16.0575(12) A, alpha = 90 degrees, beta = 98.762(3) degrees, gamma = 90 degrees, Z = 4. Solution phase NMR spectroscopic characterization of this same complex showed a highly symmetric species, consistent with a fluxional coordination environment for these compounds. Preliminary studies into the initiation of epsilon-caprolactone ring-opening polymerization using these complexes indicate high activity, producing high molecular weight polymer.     

Theoretical study of geometry and nucleophilicity of the exocyclic methylene in five-membered ring cyclic ketene acetals,neutral and protonated,containing pnictogen and chalcogen heteroatoms

A series of neutral and protonated five-membered ring cyclic ketene acetals have been examined computationally for any trends in nucleophilicity in the exocyclic methylene and for their ground state geometries. A total of 58 different species were examined, 29 neutral molecules and the corresponding 29 protonated species. The heteroatoms that were used in the heterocyclic ring were a combination of nitrogen, phosphorus, and arsenic from the pnictogen family and oxygen, sulfur, and selenium from the chalcogen family. All geometries were initially optimized at using density functional theory and all stationary points were confirmed to be either minima or transition states through vibrational analysis. All the geometries were consequentially optimized using Møller–Plesset second order perturbation theory with a polarized triple zeta basis set. The main focus of the study was the nucleophilicity of the exocyclic methylene carbon atom and its dependence on heteroatom substitution. As probes for nucleophilicity, the proton affinities of the neutral species, the bond lengths of the exocyclic double bond, and atomic charges were used. The study also resulted in some interesting molecular geometries.     

Syntheses and Crystal Structures of BaAgTbS3, BaCuGdTe3, BaCuTbTe3, BaAgTbTe3, and CsAgUTe3

Five new quaternary chalcogenides of the 1113 family, namely BaAgTbS₃, BaCuGdTe₃, BaCuTbTe₃, BaAgTbTe₃, and CsAgUTe₃, were synthesized by the reactions of the elements at 1173–1273 K. For CsAgUTe₃ CsCl flux was used. Their crystal structures were determined by single‐crystal X‐ray diffraction studies. The sulfide BaAgTbS₃ crystallizes in the BaAgErS₃ structure type in the monoclinic space group C³,_2h‐C2/m, whereas the tellurides BaCuGdTe₃, BaCuTbTe₃, BaAgTbTe₃, and CsAgUTe₃ crystallize in the KCuZrS₃ structure type in the orthorhombic space group D¹_,2⁷_,h‐Cmcm. The BaAgTbS₃ structure consists of edge‐sharing [TbS₆^9–] octahedra and [AgS₅^9–] trigonal pyramids. The connectivity of these polyhedra creates channels that are occupied by Ba atoms. The telluride structure features ²_∞[MLnTe₃^2–] layers for BaCuGdTe₃, BaCuTbTe₃, BaAgTbTe₃, and ²_∞[AgUTe₃^1–] layers for CsAgUTe₃. These layers comprise [MTe₄] tetrahedra and [LnTe₆] or [UTe₆] octahedra. Ba or Cs atoms separate these layers. As there are no short Q ··· Q (Q = S or Te) interactions these compounds achieve charge balance as Ba²⁺M⁺Ln³⁺(Q^2–)₃ (Q = S and Te) and Cs⁺Ag⁺U⁴⁺(Te^2–)₃.     

Approximate Solutions to the Time-Invariant Hamilton–Jacobi–Bellman Equation

In this paper, we develop a new method to approximate the solution to the Hamilton–Jacobi–Bellman (HJB) equation which arises in optimal control when the plant is modeled by nonlinear dynamics. The approximation is comprised of two steps. First, successive approximation is used to reduce the HJB equation to a sequence of linear partial differential equations. These equations are then approximated via the Galerkin spectral method. The resulting algorithm has several important advantages over previously reported methods. Namely, the resulting control is in feedback form and its associated region of attraction is well defined. In addition, all computations are performed off-line and the control can be made arbitrarily close to optimal. Accordingly, this paper presents a new tool for designing nonlinear control systems that adhere to a prescribed integral performance criterion.     

Tandem reactions of 1,3-diacid chlorides with 2-methylimidazoline and 2-methyl-1,4,5,6-tetrahydropyrimidine: one-pot synthesis of 1,8-naphthyridinetetraones

The reactions of 2-methylimidazoline and 2-methyl-1,4,5,6-tetrahydropyrimidine with 1,3-diacid chlorides, in the presence of Et3N in refluxing MeCN give highly functionalized potentially bioactive 1,8-naphthyridinetetraones. 2-Methylimidazoline and 2-methyl-1,4,5,6-tetrahydropyrimidine can be viewed as tridentate nucleophiles which give four consecutive tandem nucleophilic attacks on electrophiles.     

D2-m-carborane-siloxanes. III. Preparation and properties of trifluoropropyl-modified polymers

Linear D₂-m-carborane-siloxanes with one, two, and three trifluoropropyl moieties per repeat unit were prepared by the condensation reaction between bisureidosilanes and carborane disilanol. Molecular weights between 100,000 and 220,000 were obtained. Compared to fluorosilicones, the trifluoropropyl-modified carborane-siloxanes exhibited greater thermal and oxidative stability and in certain cases comparable solvent resistance. The swelling index for carborane-siloxane elastomers decreased with increasing trifluoropropyl content, although this fluorocarbon moiety did compromise the thermal stability of the carborane system.     

The synthesis of structural analogues of the podophyllum lignans: selective wittig reactions on 1-aryl-2-methyl-tetrahydronaphthoic acid anhydride

The title anhydride reacts with stabilised phosphorus ylids exclusively at the carbonyl remote from the 1-aryl substituent. These products have been converted into a variety of compounds related in structure to deoxyisopicrophyllotoxin.     

Rotational-translattonal energy exchange in molecule-surface collisions

Reported are calculations of rotational energy transfer in collisions of Cl₂ molecules with a rigid, smooth surface, using both sudden approximations and quasi-classical trajectories. High probabilities are found for very large Δj transitions compared to corresponding gas-phase collisions: thus molecular collisions with walls can be extremely efficient in producing rotational transitions.