Stille Cross‐Coupling of a Racemic Planar‐Chiral Ferrocene and Crystallographic Trace Analysis of Catalysis Intermediates and By‐products

A pressure‐controlled procedure for the S_N1 reaction of rac‐1‐[(dimethylamino)methyl]‐2‐(tributylstannyl)ferrocene ( 1 ) to rac‐1‐(phthalimidomethyl)‐2‐(tributylstannyl)ferrocene ( 2 ) was developed. Pd⁰‐Catalyzed Stille coupling of 2 with iodobenzene afforded rac‐1‐phenyl‐2‐(N‐phthalimidomethyl)ferrocene ( 5 ) in 74% yield; after trace enrichment by crystallization of the combined mother liquors, one single crystal of each, 5 , catalysis intermediate trans‐iodo(σ‐phenyl)bis(triphenylarsino)palladium(II) ( 7 ), trans‐diiodobis(triphenylarsino)palladium(II) ( 8 ), and rac‐2,2′‐bis(phthalimidomethyl)‐1,1′‐biferrocene ( 9 ) could be isolated by crystal sorting under a microscope and characterized by X‐ray crystal structure analysis. Furthermore, 5 was deprotected to amine ( 11 ), which does even survive the Birch reduction to rac‐1‐(aminomethyl)‐2‐(cyclohexa‐2,5‐dienyl)ferrocene ( 12 ).     

A New Approach for the Photosynthetic Antenna–Reaction Center Complex with a Model Organized Around an s‐Triazine Linker

Two new artificial mimics of the photosynthetic antenna‐reaction center complex have been designed and synthesized (BDP‐H₂P‐C₆₀ and BDP‐ZnP‐C₆₀). The resulting electron‐donor/acceptor conjugates contain a porphyrin (either in its free‐base form (H₂P) or as Zn‐metalated complex (ZnP)), a boron dipyrrin (BDP), and a fulleropyrrolidine possessing, as substituent of the pyrrolidine nitrogen, an ethylene glycol chain terminating in an amino group C₆₀‐X‐NH₂ (X=spacer). In both cases, the three different components were connected by s‐triazine through stepwise substitution reactions of cyanuric chloride. In addition to the facile synthesis, the star‐type arrangement of the three photo‐ and redox‐active components around the central s‐triazine unit permits direct interaction between one another, in contrast to reported examples in which the three components are arranged in a linear fashion. The energy‐ and electron‐transfer properties of the resulting electron‐donor/acceptor conjugates were investigated by using UV/Vis absorption and emission spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. Comparison of the absorption spectra and cyclic voltammograms of BDP‐H₂P‐C₆₀ and BDP‐ZnP‐C₆₀ with those of BDP‐H₂P, BDP‐ZnP and BDP‐C₆₀, which were used as references, showed that the spectroscopic and electrochemical properties of the individual constituents are basically retained, although some appreciable shifts in terms of absorption indicate some interactions in the ground state. Fluorescence lifetime measurements and transient absorption experiments helped to elucidate the antenna function of BDP, which upon selective excitation undergoes a rapid and efficient energy transfer from BDP to H₂P or ZnP. This is then followed by an electron transfer to C₆₀, yielding the formation of the singlet charge‐separated states, namely BDP‐H₂P ^.+‐ C₆₀ ^.? and BDP‐ZnP ^.+‐ C₆₀ ^{. ?}. As such, the sequence of energy transfer and electron transfer in the present models mimics the events of natural photosynthesis.     

A rate of convergence for monotone finite difference approximations to fully nonlinear,uniformly elliptic PDEs

We obtain an algebraic rate of convergence for monotone and consistent finite difference approximations to Lipschitz‐continuous viscosity solutions of uniformly elliptic partial differential equations. © 2007 Wiley Periodicals, Inc.     

Synthesis of terpyridine ligands and their complexation with Zn2+ and Ru2+ for optoelectronic applications

A series of soluble conjugated ligands TT , FT , PT , and NT that contained terpyridyl terminal units were synthesized by Heck coupling. These ligands absorbed at 341–434 nm and emitted blue–green light, with maximum at 440–522 nm and photoluminescence quantum yields of 0.15–0.71 in solution. The double‐layer electroluminescent devices with the configuration of ITO/PEDOT/ligand FT , PT , or NT /Ca/Al exhibited a brightness of 43–63 cd/m². These ligands were further reacted with zinc(II) and ruthenium(II) ions and subsequent anion exchange to afford linear and supramolecular complexes. The photophysics of these complexes were investigated. A significant redshift of the emission maximum of the Zn complexes relative to the corresponding ligands was observed. The Ru complexes were used to fabricate photovoltaic devices with the structure ITO/PEDOT/Ru complex/P3HT:PCBM (1:1 wt/wt)/Ca/Al. The power conversion efficiency of these polymer–fullerene bulk heterojunction photovoltaic devices was up to 0.71%. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7702–7712, 2008     

Thorium(IV) and neptunium(V) uptake from carbonate containing aqueous solutions by HDTMA-modified natural zeolites

The ²³²Th-uptake ([Th(IV)]° = 9.7 × 10^?5 M) from carbonate solutions ([CO ₃ ² ]_tot = 0.25 M, 9.0 < pH_c < 10.8) by raw and HDTMA-modified HEU-type zeolitic-, chabazitic- and phillipsitic-tuffs was investigated. The strong uptake by the HDTMA-tuffs at pH_c≈9 was assigned to the Th(CO₃) ₅ ^6? and ThOH(CO₃) ₄ ^5? predominance. The sorption coefficients (R _d) decreased with increasing pH_c indicating carbonate competition. Enhanced R _d values for pH_c > 10.5 are likely due to ThO₂(am)-precipitation. The ²³⁷Np-uptake ([Np(V)]° = 2.6 × 10^?5 M) from carbonate solutions ([CO ₃ ² ]_tot = 0.25 and 3.0 × 10^?4 M) by raw and HDTMA-modified HEU-type zeolitic tuff and pulverized pure heulandite crystals was studied under Ar-atmosphere at 6 < pH_c < 11. The R _d values for both elements indicated the modified tuffs potential to remove tetravalent- and pentavalent actinides from environmental matrices.     

Gas-phase fragmentation characteristics of benzyl-aminated lysyl-containing tryptic peptides

The fragmentation characteristics of peptides derivatized at the side-chain ε-amino group of lysyl residues via reductive amination with benzaldehyde have been examined using collision-induced dissociation (CID) tandem mass spectrometry. The resulting MS/MS spectra exhibit peaks representing product ions formed from two independent fragmentation pathways. One pathway results in backbone fragmentation and commonly observed sequence ion peaks. The other pathway corresponds to the unsymmetrical, heterolytic cleavage of the C_ζ-N_ε bond that links the benzyl derivative to the side-chain lysyl residue. This results in the elimination of the derivative as a benzylic or tropylium carbocation and a (n − l)⁺-charged peptide product (where n is the precursor ion charge state). The frequency of occurrence of the elimination pathway increases with increasing charge of the precursor ion. For the benzylmodified tryptic peptides analyzed in this study, peaks representing products from both of these pathways are observed in the MS/MS spectra of doubly-charged precursor ions, but the carbocation elimination pathway occurs almost exclusively for triply-charged precursor ions. The experimental evidence presented herein, combined with molecular orbital calculations, suggests that the elimination pathway is a charge-directed reaction contingent upon protonation of the secondary ε-amino group of the benzyl-derivatized lysyl side chain. If the secondary ε-amine is protonated, the elimination of the carbocation is observed. If the precursor is not protonated at the secondary ε-amine, backbone fragmentation persists. The application of appropriately substituted benzyl analogs may allow for selective control over the relative abundance of product ions generated from the two pathways.     

Block-coordinate and incremental aggregated proximal gradient methods for nonsmooth nonconvex problems

Mathematical Programming - This paper analyzes block-coordinate proximal gradient methods for minimizing the sum of a separable smooth function and a (nonseparable) nonsmooth function, both of...     

Polyoxomolybdenum(V/VI)-sulfite compounds: synthesis, structural, and physical studies

Reaction of Na(2)Mo(VI)O(4) x 2H(2)O with (NH(4))(2)SO(3) in the mixed-solvent system H(2)O/CH(3)CN (pH = 5) resulted in the formation of the tetranuclear cluster (NH(4))(4)[Mo(4)(VI)SO(16)] x H(2)O (1), while the same reaction in acidic aqueous solution (pH = 5) yielded (NH(4))(4)[Mo(5)(VI)S(2)O(21)] x 3H(2)O (2). Compound {(H(2)bipy)(2)[Mo(5)(VI)S(2)O(21)] x H(2)O}(x) (3) was obtained from the reaction of aqueous acidic solution of Na(2)Mo(VI)O(4) x 2H(2)O with (NH(4))(2)SO(3) (pH = 2.5) and 4,4'-bipyridine (4,4'-bipy). The mixed metal/sulfite species (NH(4))(7)[Co(III)(Mo(2)(V)O(4))(NH(3))(SO(3))(6)] x 4H(2)O (4) was synthesized by reacting Na(2)Mo(VI)O(4) x 2H(2)O with CoCl(2) x 6H(2)O and (NH(4))(2)SO(3) with precise control of pH (5.3) through a redox reaction. The X-ray crystal structures of compounds 1, 2, and 4 were determined. The structure of compound 1 consists of a ring of four alternately face- and edge-sharing Mo(VI)O(6) octahedra capped by the trigonal pyramidal sulfite anion, while at the base of the Mo(4) ring is an oxo group which is asymmetrically shared by all four molybdenum atoms. Compound 3 is based on the Strandberg-type heteropolyion [Mo(5)(VI)S(2)O(21)](4-), and these coordinatively saturated clusters are joined by diprotonated 4,4'-H(2)bipy(2+) through strong hydrogen bonds. Compound 3 crystallizes in the chiral space group C2. The structure of compound 4 consists of a novel trinuclear [Co(III)Mo(2)(V)SO(3)(2-)] cluster. The chiral compound 3 exhibits nonlinear optical (NLO) and photoluminescence properties. The assignment of the sulfite bands in the IR spectrum of 4 has been carried out by density functional calculations. The cobalt in 4 is a d(6) octahedral low-spin metal atom as it was evidenced by magnetic susceptibility measurements, cw EPR, BVS, and DFT calculations. The IR and solid-state UV-vis spectra as well as the thermogravimetric analyses of compounds 1-4 are also reported.     

On the accuracy of the IWM–CFC approximation in differentially rotating relativistic stars

A circular restricted three-body problem describes the motion of a test particle around two massive bodies in circular orbits. In this system, orbital decay caused by a gravitational radiation reaction between the two primary bodies is considered but the direct effect of gravitational radiation on the test particle is neglected. We adopt distance- and time-scale transformations to Newtonian problems so that systems without orbital decay will not depend on separation between the primaries but systems with orbital decay will depend on this separation. If a regular or chaotic orbit is given in a Newtonian system, the starting separation of the primaries varies according to the corresponding decay system. Thus, insights into the chaotic behaviour of a third body in a decay case are provided. For a large initial separation between the primaries, the chaos that exists in a Newtonian problem may be retained for a long enough time scale of dissipative evolution before the primaries coalesce. The final state of a third body is escape attributed to orbital decay.