Borohydride complexes of rare earths,and their applications in various organic transformations

Borohydride complexes of the rare earths have attracted increasing interest during the last decade. This review aims to cover recent results over this period with respect to the preparation, characterization, structure, and applications in organic chemistry of this family of compounds, including inorganic and organometallic complexes. Special emphasis is made on their use for polymerization catalysis.     

Space and space-time longitudinal velocity correlations in the turbulent far wake of a flat plate in incompressible flow

This paper presents longitudinal space and space-time conventional velocity correlations measured in the wake of a two-dimensional flat-plate at zero incidence, with fully-turbulent boundary layers at its sharp trailing edge. Iso-correlation contour plots are given in the plane of symmetry and normal to this plane in the assumed asymptotic (in the mean velocity sense) part. Comparisons with initially laminar 2-D wake results show that the classical Double-Roller-Eddy model developed for initially laminar wakes is not adapted to initially turbulent wakes; on the other hand, comparison with supersonic wake of the same nature seems to confirm this conclusion. The lack of detailed experimental data in this field is outlined, together with the need of a refined theoretical approach to the coherent structures existing in such flows.     

Large-scale structures visualization in a high Reynolds number,turbulent flat-plate wake at supersonic speed

A visual study is performed in a supersonic, two-dimensional wake; the high value of the Reynolds number ensures that the wake is turbulent from the trailing edge. The flow is seeded by fluid vaporization in one boundary layer upstream of the trailing edge; a light sheet is generated by a Q-switched, high energy ruby laser. The set of photographs taken from the trailing edge up to the far wake is then processed after digitization of the pictures. A progressive contamination of the lower part of the wake by the fluid initially present in the upper part can be observed. In the far wake region, well organized large scale structures can be visualized. Statistics are performed and the results are compared with previous hot-wire measurements and discussed in terms of downstream wake behaviour.This paper was presented at the 9th Symposium on turbulence, University of Missouri-Rolla, October 1–3, 1984     

Reversible coordinative chain transfer polymerization of styrene by rare earth borohydrides,chlorides/dialkylmagnesium systems

The ability of various rare earth borohydride and chloride complexes/n‐butylethylmagnesium systems to operate styrene chain transfer polymerization in mild conditions has been assessed. Thirteen precatalysts have been considered: the rare earth trisborohydrides Ln(BH₄)₃(THF)_x (x = 3, Ln = Nd (1), La (2), Sm (3), x = 2, Ln = Y (4), Sc (5)), the rare earth chlorides LnCl₃(THF)_x (x = 3, Ln = Nd (6), La (7), Sm (8), Y (9), x = 2, Ln = Sc (10)), the mixed La(BH₄)₂Cl(THF)_2.6 (11) and the half‐lanthanidocenes Cp*Ln(BH₄)₂(THF)₂ (Ln = Nd (12), La (13)). Six systems were found to be active precatalysts for the polymerization of styrene. 1 , 2 , and 11 led to an efficient transmetalation of the growing polystyrene chain with the simultaneous occurrence of βH elimination, whereas 7 , 12 , and 13 led to catalyzed chain growth behavior. It is noteworthy that the catalyzed chain growth obtained with 12 and 13 occurs with significant stereoselectivity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 802–814, 2010     

The method of Gaussian weighted trajectories. V. On the 1GB procedure for polyatomic processes

In recent years, many chemical reactions have been studied by means of the quasiclassical trajectory (QCT) method within the Gaussian binning (GB) procedure. The latter consists of "quantizing" the final vibrational actions in Bohr spirit by putting strong emphasis on the trajectories reaching the products with vibrational actions close to integer values. A major drawback of this procedure is that if N is the number of product vibrational modes, the amount of trajectories necessary to converge the calculations is ～10(N)×larger than with the standard QCT method. Applying it to polyatomic processes is thus problematic. In a recent paper, however, Czako? and Bowman propose to quantize the total vibrational energy instead of the vibrational actions [G. Czako? and J. M. Bowman, J. Chem. Phys. 131, 244302 (2009)], a procedure called 1GB here. The calculations are then only ～10 times more time consuming than with the standard QCT method, allowing thereby for considerable numerical saving. In this paper, we propose some theoretical arguments supporting the 1GB procedure and check its validity on model test cases as well as the prototype four-atom reaction OH+D(2)→HOD+D.     

Coexistence of Two Thermally Induced Intramolecular Electron Transfer Processes in a Series of Metal Complexes [M(Cat‐N‐BQ)(Cat‐N‐SQ)]/[M(Cat‐N‐BQ)2] (M=Co,Fe, and Ni) bearing Non‐Innocent Catechol‐Based Ligands: A Combined Experimental and Theoretical Study

The different thermally induced intermolecular electron transfer (IET) processes that can take place in the series of complexes [M(Cat‐N‐BQ)(Cat‐N‐SQ)]/[M(Cat‐N‐BQ)₂], for which M=Co ( 2 ), Fe ( 3 ) and Ni( 4 ), and Cat‐N‐BQ and Cat‐N‐SQ denote the mononegative (Cat‐N‐BQ^?) or dinegative (Cat‐N‐SQ^2?) radical forms of the tridentate Schiff‐base ligand 3,5‐di‐tert‐butyl‐1,2‐quinone‐1‐(2‐hydroxy‐3,5‐di‐tert‐butylphenyl)imine, have been studied by variable‐temperature UV/Vis and NMR spectroscopies. Depending on the metal ion, rather different behaviors are observed. Complex 2 has been found to be one of the few examples so far reported to exhibit the coexistence of two thermally induced electron transfer processes, ligand‐to‐metal (IET^LM) and ligand‐to‐ligand (IET^LL). IET^LL was only found to take place in complex 3 , and no IET was observed for complex 4 . Such experimental studies have been combined with ab initio wavefunction‐based CASSCF/CASPT2 calculations. Such a strategy allows one to solicit selectively the speculated orbitals and to access the ground states and excited‐spin states, as well as charge‐transfer states giving additional information on the different IET processes.     

Topological sensitivity of energy cost functional for wave-based defect identification

This article is concerned with establishing the topological sensitivity (TS) against the nucleation of small trial inclusions of an energy-like cost function. The latter measures the discrepancy between two time-harmonic elastodynamic states (respectively defined, for cases where overdetermined boundary data is available for identification purposes, in terms of Dirichlet or Neumann boundary data for the same reference solid) as the strain energy of their difference. Such cost function constitutes a particular form of error in constitutive relation and may be used for e.g. defect identification. The TS is expressed in terms of four elastodynamic fields, namely the free and adjoint solutions for Dirichlet or Neumann data. A similar result is also given for the linear acoustic scalar case. A synthetic numerical example where the TS result is used for the qualitative identification of an inclusion is presented for a simple 2D acoustic configuration.     

Experimental characterization of an Yb-doped fiber ring laser with frequency-shifted feedback

We present experimental characteristics of an Yb³⁺-doped fiber ring laser operating with frequency-shifted feedback (FSF) through an acousto-optic modulator (AOM) and seeded by both a stationary continuous-wave (CW) laser and spontaneous emission. We show the spectrum and output characteristics for operations with several effective gain bandwidths, as established by Fabry-Perot etalons inside the cavity. Observation using a high finesse Fabry-Perot interferometer shows that, as expected from earlier work, although the spectrum of the FSF laser without seeding is continuous, when seeded by a CW-laser the spectrum consists of a comb of discrete modes, each offset from the seed by an integer number of AOM frequency shifts. The experimental results are in excellent quantitative agreement with the theory developed earlier [L. Yatsenko, B.W. Shore, K. Bergmann, Opt. Commun. 236 (2004) 183].