A finite point method for adaptive three-dimensional compressible flow calculation

The Finite Point Method (FPM) is a meshless technique which is based on both, a Weighted Least-Squares numerical approximation on local clouds of points and a collocation technique which allows obtaining the discrete system of equations. The research work we present is part of a major investigation into the capabilities of the FPM to deal with threedimensional applications concerning real compressible fluid flow problems. In the first part of this work, the upwind biased scheme employed for solving the flow equations is described. Secondly, with the aim of exploiting meshless capabilities, an h-adaptive methodology for two and three-dimensional compressible flow calculations is developed. This adaptive technique applies a solution-based indicator in order to identify local clouds where new points should be inserted in or existing points could be safely removed from the computational domain. The flow solver and the adaptive procedure have been evaluated and the results are highly encouraging. Several numerical examples are provided throughout the article in order to illustrate their performance

Development and applications of the finite point method to compressible aerodynamics problems

This work deals with the development and application of the Finite Point Method (FPM) to compressible aerodynamics problems. The research focuses mainly on investigating the capabilities of the meshless technique to address practical problems, one of the most outstanding issues in meshless methods. The FPM spatial approximation is studied firstly, with emphasis on aspects of the methodology that can be improved to increase its robustness and accuracy. Suitable ranges for setting the relevant approximation parameters and the performance likely to be attained in practice are determined. An automatic procedure to adjust the approximation parameters is also proposed to simplify the application of the method, reducing problem- and user-dependence without affecting the flexibility of the meshless technique. The discretization of the flow equations is carried out following wellestablished approaches, but drawing on the meshless character of the methodology. In order to meet the requirements of practical applications, the procedures are designed and implemented placing emphasis on robustness and efficiency (a simplification of the basic FPM technique is proposed to this end). The flow solver is based on an upwind spatial discretization of the convective fluxes (using the approximate Riemann solver of Roe) and an explicit time integration scheme. Two additional artificial diffusion schemes are also proposed to suit those cases of study in which computational cost is a major concern. The performance of the flow solver is evaluated in order to determine the potential of the meshless approach. The accuracy, computational cost and parallel scalability of the method are studied in comparison with a conventional FEM-based technique. Finally, practical applications and extensions of the flow solution scheme are presented. The examples provided are intended not only to show the capabilities of the FPM, but also to exploit meshless advantages. Automatic hadaptive procedures, moving domain and fluid-structure interaction problems, as well as a preliminary approach to solve high-Reynolds viscous flows, are a sample of the topics explored. All in all, the results obtained are satisfactorily accurate and competitive in terms of computational cost (if compared with a similar mesh-based implementation). This indicates that meshless advantages can be exploited with efficiency and constitutes a good starting point towards more challenging applications

Osmium-mediated direct C–H bond activation at the 8-position of quinolines

Metal-mediated direct C–H bond activation at the 8-position of quinolines, which is the essential step for the functionalization of this bond, is promoted by the hexahydride OsH6(PiPr3)2. This complex activates quinoline and 2-, 3-, 6-, and 7-methylquinoline to afford the classical trihydride derivatives OsH3{κ2-C8,N-(quinolinyl)}(PiPr3)2 and OsH3{κ2-C8,N-(quinolinyl-n-Me)}(PiPr3)2 (n = 2, 3, 6, 7), containing a four-membered heterometalla ring.Financial support from the MINECO of Spain (Projects CTQ2014-52799-P and CTQ2014-51912-REDC), the Diputación General de Aragón (E-35), FEDER, and the European Social Fund is acknowledged.Peer reviewe

A-posteriori error estimation for the finite point method with applications to compressible flow (preprint)

An a-posteriori error estimate with application to inviscid compressible flow problems is presented. The estimate is a surrogate measure of the discretization error, obtained from an approximation to the truncation terms of the governing equations. This approximation is calculated from the discrete nodal differential residuals using a reconstructed solution field on a modified stencil of points. Both the error estimation methodology and the flow solution scheme are implemented using the Finite Point Method, a meshless technique enabling higher-order approximations and reconstruction procedures on general unstructured discretizations. The performance of the proposed error indicator is studied and applications to adaptive grid refinement are presented

Azolium Control of the Osmium-Promoted Aromatic C-H Bond Activation in 1, 3-Disubstituted Substrates

The hexahydride complex OsH6((PPr3)-Pr-i)(2) promotes the C-H bond activation of the 1, 3-disubstituted phenyl group of the [BF4](-) and [BPh4](-) salts of the cations 1-(3-(isoquinolin-1-yl)phenyl)-3-methylimidazolium and 1-(3-(isoquinolin-1-yl)phenyl)-3-meth-ylbenzimidazolium. The reactions selectively afford neutral and cationic trihydride-osmium(IV) derivatives bearing kappa(2)-C, N- or kappa(2)-C, C-chelating ligands, a cationic dihydride-osmium(IV) complex stabilized by a kappa(3)-C, C, N-pincer group, and a bimetallic hexahydride formed by two trihydride-osmium(IV) fragments. The metal centers of the hexahydride are separated by a bridging ligand, composed of kappa(2)-C, N- and kappa(2)-C, C-chelating moieties, which allows electronic communication between the metal centers. The wide variety of obtained compounds and the high selectivity observed in their formation is a consequence of the main role of the azolium group during the activation and of the existence of significant differences in behavior between the azolium groups. The azolium role is governed by the anion of the salt, whereas the azolium behavior depends upon its imidazolium or benzimidazolium nature. While [BF4](-) inhibits the azolium reactions, [BPh4](-) favors the azolium participation in the activation process. In contrast to benzimidazolylidene, the imidazolylidene resulting from the deprotonation of the imidazolium substituent coordinates in an abnormal fashion to direct the phenyl C-H bond activation to the 2-position. The hydride ligands of the cationic dihydride-osmium(IV) pincer complex display intense quantum mechanical exchange coupling. Furthermore, this salt is a red phosphorescent emitter upon photoexcitation and displays a noticeable catalytic activity for the dehydrogenation of 1-phenylethanol to acetophenone and of 1, 2-phenylenedimethanol to 1-isobenzofuranone. The bimetallic hexahydride shows catalytic synergism between the metals, in the dehydrogenation of 1, 2, 3, 4-tetrahydroisoquinoline and alcohols

An adaptive finite point method for the shallow water equations

An adaptive Finite Point Method (FPM) for solving shallow water problems is presented. The numerical methodology we propose, which is based on weighted‐least squares approximations on clouds of points, adopts an upwind‐biased discretization for dealing with the convective terms in the governing equations. The viscous and source terms are discretized in a pointwise manner and the semi‐discrete equations are integrated explicitly in time by means of a multi‐stage scheme. Moreover, with the aim of exploiting meshless capabilities, an adaptive h‐refinement technique is coupled to the described flow solver. The success of this approach in solving typical shallow water flows is illustrated by means of several numerical examples and special emphasis is placed on the adaptive technique performance. This has been assessed by carrying out a numerical simulation of the 26th December 2004 Indian Ocean tsunami with highly encouraging results. Overall, the adaptive FPM is presented as an accurate enough, cost‐effective tool for solving practical shallow water problems. Copyright © 2011 John Wiley & Sons, Ltd

mer, fac, and bidentate coordination of an alkyl-POP ligand in the chemistry of nonclassical osmium hydrides

Nonclassical and classical osmium polyhydrides containing the diphosphine 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene (xant(PiPr2)2), coordinated in κ3-mer, κ3-fac, and κ2-P,P fashions, have been isolated during the cyclic formation of H2 by means of the sequential addition of H+ and H– or H– and H+ to the classical trihydride OsH3Cl{xant(PiPr2)2} (1). This complex adds H+ to form the compressed dihydride dihydrogen complex [OsCl(H···H)(η2-H2){xant(PiPr2)2}]+ (2). Under argon, cation 2 loses H2 and the resulting unsaturated fragment dimerizes to give [(Os(H···H){xant(PiPr2)2})2(μ-Cl)2]2+ (3). During the transformation the phosphine changes its coordination mode from mer to fac. The benzofuran counterpart of 1, OsH3Cl{dbf(PiPr2)2} (4; dbf(PiPr2)2 = 4,6-bis(diisopropylphosphino)dibenzofuran), also adds H+ to afford the benzofuran counterpart of 2, [OsCl(H···H)(η2-H2){xant(PiPr2)2}]+ (5), which in contrast to the latter is stable and does not dimerize. Acetonitrile breaks the chloride bridge of 3 to form the dihydrogen [OsCl(η2-H2)(CH3CN){xant(PiPr2)2}]+ (6), regenerating the mer coordination of the diphosphine. The hydride ion also breaks the chloride bridge of 3. The addition of KH to 3 leads to 1, closing a cycle for the formation of H2. Complex 1 reacts with a second hydride ion to give OsH4{xant(PiPr2)2} (7) as consequence of the displacement of the chloride. Similarly to the latter, the oxygen atom of the mer-coordinated diphosphine of 7 has a tendency to be displaced by the hydride ion. Thus, the addition of KH to 7 yields [OsH5{xant(PiPr2)2}]− (8), containing a κ2-P,P-diphosphine. Complex 8 is easily protonated to afford OsH6{xant(PiPr2)2} (9), which releases H2 to regenerate 7, closing a second cycle for the formation of molecular hydrogen.Financial support from the MINECO of Spain (Projects CTQ2014-52799-P and CTQ2014-51912-REDC), Gobierno de Aragon (E35), FEDER, and the European Social Fund is acknowledged.Peer reviewe

Square-planar alkylidyne–osmium and five-coordinate alkylidene–osmium complexes: controlling the transformation from hydride-alkylidyne to alkylidene

This is an open access article published under an ACS AuthorChoice License.Square-planar alkylidyne and five-coordinate alkylidene mixed iPr3P–Os–IPr (IPr = 1,3-bis(diisopropylphenyl)imidazolylidene) complexes have been discovered and characterized, and their formation has been rationalized. The cationic five-coordinate hydride-alkylidyne compounds [OsHX(≡CPh)(IPr)(PiPr3)]OTf (X = Cl (1), F (4); OTf = CF3SO3) undergo deprotonation with KOtBu to afford the trans-halide-alkylidyne square-planar derivatives OsX(≡CPh)(IPr)(PiPr3) (X = Cl (2), F (5)). Oxidative addition of the C(sp)–H bond of phenylacetylene and methyl propiolate along the Cl–Os–CPh axis of 2 with the hydrogen atom directed to the alkylidyne leads to alkynyl-cis-hydride-alkylidyne intermediates, which rapidly evolve into the five-coordinate alkylidene complexes Os(C≡CR)Cl(═CHPh)(IPr)(PiPr3) (R = Ph (6), CO2Me (7)) as a consequence of the migration of the hydride from the metal center to the Cα atom of the alkylidyne. Oxidative addition of the C(sp)–H bond of methyl propiolate along the X–Os–CPh axis of 2 and 5 with the hydrogen atom directed to the halide gives the alkynyl-trans-hydride-alkylidyne derivatives OsH(C≡CCO2Me)X(≡CPh)(IPr)(PiPr3) (X = Cl (8), F (9)). Complex 8 evolves into 7. However, complex 9 containing the stronger π-donor fluoride is stable. The oxidative addition of HCl to 2 selectively yields the cis-hydride-alkylidyne compound OsHCl2(≡CPh)(IPr)(PiPr3) (10), which is also stable.Financial support from the Spanish MINECO (Projects CTQ2014-52799-P, Red de Excelencia Consolider CTQ2014-51912-REDC), the DGA (E35), and the European Social Fund (FSE) is acknowledged. J.J.F.C. acknowledges support via a predoctoral fellowship from the DGA.Peer reviewe

A finite point method for adaptive three-dimensional compressible flow calculation

The Finite Point Method (FPM) is a meshless technique which is based on both, a Weighted Least-Squares numerical approximation on local clouds of points and a collocation technique which allows obtaining the discrete system of equations. The research work we present is part of a major investigation into the capabilities of the FPM to deal with threedimensional applications concerning real compressible fluid flow problems. In the first part of this work, the upwind biased scheme employed for solving the flow equations is described. Secondly, with the aim of exploiting meshless capabilities, an h-adaptive methodology for two and three-dimensional compressible flow calculations is developed. This adaptive technique applies a solution-based indicator in order to identify local clouds where new points should be inserted in or existing points could be safely removed from the computational domain. The flow solver and the adaptive procedure have been evaluated and the results are highly encouraging. Several numerical examples are provided throughout the article in order to illustrate their performance.Preprin

Selective C–Cl bond oxidative addition of chloroarenes to a POP–rhodium complex

The C–Cl bond cis oxidative addition of 12 chloroarenes, including chlorobenzene, chlorotoluenes, chlorofluorobenzenes, and di- and trichlorobenzenes to RhH{xant(PiPr2)2} (1; xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) and the ability of the resulting rhodium(III) species to undergo reductive elimination reactions are reported. Complex 1 reacts with chlorobenzene to give RhHCl(C6H5){xant(PiPr2)2} (2), which eliminates benzene to afford RhCl{xant(PiPr2)2} (3). On the other hand, in the presence of potassium tert-butoxide (KOtBu), it undergoes dehydrodechlorination to yield Rh(C6H5){xant(PiPr2)2} (4). The reactions of 1 with 3- and 4-chlorotoluenes lead to RhHCl(C6H4-3-Me){xant(PiPr2)2} (5) and RhHCl(C6H4-4-Me){xant(PiPr2)2} (6), respectively. Treatment of the acetone solutions of both compounds with KOtBu also results in their dehydrodechlorination to give Rh(C6H4-3-Me){xant(PiPr2)2} (7) and Rh(C6H4-4-Me){xant(PiPr2)2} (8). Chlorofluorobenzenes undergo both C–Cl oxidative addition and C–H bond activation in a competitive manner. The amount of the C–H activation product increases as fluorine and chlorine are separated. Complex 1 reacts with o-chlorofluorobenzene to afford the C–Cl oxidative addition product RhHCl(C6H4-2-F){xant(PiPr2)2} (9). The reaction of 1 with m-chlorofluorobenzene leads to RhHCl(C6H4-3-F){xant(PiPr2)2} (10; 91%) and the C–H bond activation product Rh(C6H3-2-Cl-6-F){xant(PiPr2)2} (12; 9%), whereas p-chlorofluorobenzene gives a mixture of RhHCl(C6H4-4-F){xant(PiPr2)2} (13; 61%) and Rh(C6H3-3-Cl-6-F){xant(PiPr2)2} (15; 39%). The addition of KOtBu to the acetone solutions of 9, 10, and 13 produces the HCl abstraction and the formation of Rh(C6H4-2-F){xant(PiPr2)2} (16), Rh(C6H4-3-F){xant(PiPr2)2} (17), and Rh(C6H4-4-F){xant(PiPr2)2} (18). In contrast to o-chlorofluorobenzene, 1,2-dichlorobenzene reacts with 1 to give RhHCl(C6H4-2-Cl){xant(PiPr2)2} (19; 32%), Rh(C6H4-2-Cl){xant(PiPr2)2} (20; 51%) and Rh(C6H3-2,3-Cl2){xant(PiPr2)2} (22; 17%). The reactions of 1 with 1,3- and 1,4-dichlorobenzene lead to the respective C–Cl bond oxidative addition products RhHCl(C6H4-3-Cl){xant(PiPr2)2} (23) and RhHCl(C6H4-4-Cl){xant(PiPr2)2} (24), which afford Rh(C6H4-3-Cl){xant(PiPr2)2} (25) and Rh(C6H4-4-Cl){xant(PiPr2)2} (26) by dehydrodechlorination with KOtBu in acetone. Treatment of 1 with 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzenes leads to RhHCl(C6H3-2,3-Cl2){xant(PiPr2)2} (27), RhHCl(C6H3-3,4-Cl2){xant(PiPr2)2} (28), and RhHCl(C6H3-3,5-Cl2){xant(PiPr2)2} (29). The addition of KOtBu to acetone solutions of 27-29 affords 22, Rh(C6H3-3,4-Cl2){xant(PiPr2)2} (30) and Rh(C6H3-3,5-Cl2){xant(PiPr2)2} (31).Financial support from the MINECO of Spain (Projects CTQ2014-52799-P and CTQ2014-51912-REDC), the Diputacion General de Aragon (E-35), FEDER, and the European Social Fund is acknowledged.Peer reviewe