Coordination Chemistry of Gold Catalysts in Solution: A Detailed NMR Study

Coordination chemistry of gold catalysts bearing eight different ligands [L=PPh₃, JohnPhos (L2), Xphos (L3), DTBP, IMes, IPr, dppf, S‐tolBINAP (L8)] has been studied by NMR spectroscopy in solution at room temperature. Cationic or neutral mononuclear complexes LAuX (L=L2, L3, IMes, IPr; X=charged or neutral ligand) underwent simple ligand exchange without giving any higher coordinate complexes. For L2AuX the following ligand strength series was determined: MeOH?hex‐3‐yne <MeCN≈OTf^??Me₂S<2,6‐lutidine<4‐picoline<CF₃CO₂^?≈DMAP<TMTU<PPh₃<OH^?≈Cl^?. Some heteroligand complexes DTBPAuX exist in solution in equilibrium with the corresponding symmetrical species. Binuclear complexes dppf(AuOTf)₂ and S‐tolBINAP(AuOTf)₂ showed different behavior in exchange reactions with ligands depending on the ligand strength. Thus, PPh₃ causes abstraction of one gold atom to give mononuclear complexes LLAuPPh₃⁺ and (Ph₃P)_nAu⁺, but other N and S ligands give ordinary dicationic species LL(AuNu)₂²⁺. In reactions with different bases, LAu⁺ provided new oxonium ions whose chemistry was also studied: (DTBPAu)₃O⁺, (L2Au)₂OH⁺, (L2Au)₃O⁺, (L3Au)₂OH⁺, and (IMesAu)₂OH⁺. Ultimately, formation of gold hydroxide LAuOH (L=L2, L3, IMes) was studied. Ligand‐ or base‐assisted interconversions between (L2Au)₂OH⁺, (L2Au)₃O⁺, and L2AuOH are described. Reactions of dppf(AuOTf)₂ and S‐tolBINAP(AuOTf)₂ with bases provided more interesting oxonium ions, whose molecular composition was found to be [dppf(Au)₂]₃O₂²⁺, L8(Au)₂OH⁺, and [L8(Au)₂]₃O₂²⁺, but their exact structure was not established. Several reactions between different oxonium species were conducted to observe mixed heteroligand oxonium species. Reaction of L2AuNCMe⁺ with S^2? was studied; several new complexes with sulfide are described. For many reversible reactions the corresponding equilibrium constants were determined.     

Generalized coulomb barrier transmission coefficient for solar neutrino and astrophysical problems

For astrophysical calculations, it is customary to extrapolate higher-energy (20keV) data using the Gamow transmission coefficient in estimating the nonresonance nuclear fusion reaction cross sections (E) for charged particles at low energies (<20 keV). We present a general extrapolation method based on a more realistic Coulomb barrier transmission coefficient, which can accommodate simultaneously both nonresonance and resonance contributions.     

Experimental upper limits for hadronic and axion decays of the γ(1S)

A search for the decays γ→ρπ, γ→J/ψX and γ→γa (whereX is undetermined and a is an axion) has been completed using the LENA detector at the DORIS storage ring. No evidence for any of these processes was found. For these decay modes we set branching fraction upper limits (90% C.L.) of 2.1×10^?3, 2.0×10^?2 and 9.1×10^?4, respectively.     

Concurrent stochastic methods for global optimization

The global optimization problem, finding the lowest minimizer of a nonlinear function of several variables that has multiple local minimizers, appears well suited to concurrent computation. This paper presents a new parallel algorithm for the global optimization problem. The algorithm is a stochastic method related to the multi-level single-linkage methods of Rinnooy Kan and Timmer for sequential computers. Concurrency is achieved by partitioning the work of each of the three main parts of the algorithm, sampling, local minimization start point selection, and multiple local minimizations, among the processors. This parallelism is of a coarse grain type and is especially well suited to a local memory multiprocessing environment. The paper presents test results of a distributed implementation of this algorithm on a local area network of computer workstations. It also summarizes the theoretical properties of the algorithm.Research supported by AFOSR grant AFOSR-85-0251, ARO contract DAAG 29-84-K-0140, NSF grant DCR-8403483, and NSF cooperative agreement DCR-8420944.     

The umbral calculus and orthogonal polynomials

We determine all orthogonal polynomials having Boas-Buck generating functions g(t)(xf(t)), where% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacqqHOo% qwcaGGOaGaamiDaiaacMcacqGH9aqpruqqYLwySbacfaGaa8hiamaa% BeaaleaacaaIWaaabeaakiaadAeacaqGGaWaaSbaaSqaaiaabgdaae% qaaOGaaeikaiaadggacaGGSaGaa8hiaiaadshacaqGPaGaaeilaiaa% bccacaqGGaGaaeiiaiaadggacqGHGjsUcaaIWaGaaiilaiaa-bcacq% GHsislcaaIXaGaaiilaiaa-bcacqGHsislcaaIYaGaaiilaiablAci% ljaacUdaaeaacqqHOoqwcaGGOaGaamiDaiaacMcacqGH9aqpcaWFGa% WaaSraaSqaaiaaicdaaeqaaOGaamOraiaabccadaWgaaWcbaGaaeOm% aaqabaGccaGGOaWaaSqaaSqaaiaaigdaaeaacaaIZaaaaOGaaiilai% aa-bcadaWcbaWcbaGaaGOmaaqaaiaaiodaaaGccaGGSaGaa8hiaiaa% dshacaGGPaGaa8hiamaaBeaaleaacaaIWaaabeaakiaadAeacaqGGa% WaaSbaaSqaaiaabkdaaeqaaOGaaeikamaaleaaleaacaaIYaaabaGa% aG4maaaakiaacYcacaWFGaWaaSqaaSqaaiaaisdaaeaacaaIZaaaaO% Gaaiilaiaa-bcacaWG0bGaaiykaiaacYcacaWFGaWaaSraaSqaaiaa% icdaaeqaaOGaamOraiaabccadaWgaaWcbaGaaeOmaaqabaGccaGGOa% WaaSqaaSqaaiaaisdaaeaacaaIZaaaaOGaaiilaiaa-bcadaWcbaWc% baGaaGynaaqaaiaaiodaaaGccaGGSaGaa8hiaiaadshacaGGPaGaai% 4oaaqaaiabfI6azjaacIcacaWG0bGaaiykaiabg2da9iaa-bcadaWg% baWcbaGaaGimaaqabaGccaWGgbGaaeiiamaaBaaaleaacaqGZaaabe% aakiaacIcadaWcbaWcbaGaaGymaaqaaiaaisdaaaGccaGGSaGaa8hi% amaaleaaleaacaaIYaaabaGaaGinaaaakiaacYcacaWFGaWaaSqaaS% qaaiaaiodaaeaacaaI0aaaaOGaaiilaiaa-bcacaWG0bGaaiykaiaa% -bcadaWgbaWcbaGaaGimaaqabaGccaWGgbGaaeiiamaaBaaaleaaca% qGZaaabeaakiaabIcadaWcbaWcbaGaaGOmaaqaaiaaisdaaaGccaGG% SaGaa8hiamaaleaaleaacaaIZaaabaGaaGinaaaakiaacYcacaWFGa% WaaSqaaSqaaiaaiwdaaeaacaaI0aaaaOGaaiilaiaa-bcacaWG0bGa% aiykaiaacYcaaeaadaWgbaWcbaGaaGimaaqabaGccaWGgbGaaeiiam% aaBaaaleaacaqGZaaabeaakiaacIcadaWcbaWcbaGaaG4maaqaaiaa% isdaaaGccaGGSaGaa8hiamaaleaaleaacaaI1aaabaGaaGinaaaaki% aacYcacaWFGaWaaSqaaSqaaiaaiAdaaeaacaaI0aaaaOGaaiilaiaa% -bcacaWG0bGaaiykaiaacYcacaGGUaGaa8hiamaaBeaaleaacaaIWa% aabeaakiaadAeacaqGGaWaaSbaaSqaaiaabodaaeqaaOGaaeikamaa% leaaleaacaaI1aaabaGaaGinaaaakiaacYcacaWFGaWaaSqaaSqaai% aaiAdaaeaacaaI0aaaaOGaaiilaiaa-bcadaWcbaWcbaGaaG4naaqa% aiaaisdaaaGccaGGSaGaa8hiaiaadshacaGGPaGaaiOlaaaaaa!C1F3!\[\begin{gathered}\Psi (t) = {}_0F{\text{ }}_{\text{1}} {\text{(}}a, t{\text{), }}a \ne 0, - 1, - 2, \ldots ; \hfill \\\Psi (t) = {}_0F{\text{ }}_{\text{2}} (\tfrac{1}{3}, \tfrac{2}{3}, t) {}_0F{\text{ }}_{\text{2}} {\text{(}}\tfrac{2}{3}, \tfrac{4}{3}, t), {}_0F{\text{ }}_{\text{2}} (\tfrac{4}{3}, \tfrac{5}{3}, t); \hfill \\\Psi (t) = {}_0F{\text{ }}_{\text{3}} (\tfrac{1}{4}, \tfrac{2}{4}, \tfrac{3}{4}, t) {}_0F{\text{ }}_{\text{3}} {\text{(}}\tfrac{2}{4}, \tfrac{3}{4}, \tfrac{5}{4}, t), \hfill \\{}_0F{\text{ }}_{\text{3}} (\tfrac{3}{4}, \tfrac{5}{4}, \tfrac{6}{4}, t),. {}_0F{\text{ }}_{\text{3}} {\text{(}}\tfrac{5}{4}, \tfrac{6}{4}, \tfrac{7}{4}, t). \hfill \\\end{gathered}\]We also determine all Sheffer polynomials which are orthogonal on the unit circle. The formula for the product of polynomials of the Boas-Buck type is obtained.     

Computing singular solutions to nonlinear analytic systems

Summary A method to generate an accurate approximation to a singular solution of a system of complex analytic equations is presented. Since manyreal systems extend naturally tocomplex analytic systems, this porvides a method for generating approximations to singular solutions to real systems. Examples include systems of polynomials and systems made up of trigonometric, exponential, and polynomial terms. The theorem on which the method is based is proven using results from several complex variables. No special conditions on the derivatives of the system, such as restrictions on the rank of the Jacobian matrix at the solution, are required. The numerical method itself is developed from techniques of homotopy continuation and 1-dimensional quadrature. A specific implementation is given, and the results of numerical experiments in solving five test problems are presented.