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La gestion de la innovacion para obtener beneficios es una cuestion compleja. No obstante, algunos enfoques pueden ayudar a los directivos a la hora de centrarse en lo basico. Las acciones de gestion, tanto si proceden de empresas grandes como si proceden de empresas pequenas, en diversas ocasiones pueden configurar el papel de la propiedad intelectual y de la propia tecnologia a la hora de definir el sistema de apropiabilidad y la arquitectura del sector. El marco que se desarrolla en este articulo puede permitir tanto a los teoricos como a los directivos considerar la estrategia tecnologica de una forma mas amplia.
In a previous study (Barham et al 2007 Acta Mech. 191 1–19), the finite deformation of a circular magnetoelastic membrane in an axisymmetric dipole field was calculated by specializing the equations of three-dimensional magnetoelastic equilibrium. The predicted response was found to be similar to the classical limit-point instability occurring in analogous purely mechanical problems. A limit-point instability occurs under conditions corresponding to the incipient non-existence of equilibria. Under such conditions the body is necessarily on the verge of a dynamical state. In the present setting, this corresponds to the occurrence of a maximum in the equilibrium deflection of the membrane with respect to applied field strength and proximity of the field source. The earlier conjecture of a limit-point instability, advanced in Barham et al (2007 Acta Mech. 191 1–19), is confirmed in the present work by using a variational method based on an adaptation of the energy criterion of elastic stability to the magnetoelastic setting.
The platinum ethylene complexes (PyPyr)Pt(C2H4)Cl (1) and (PyPyr)Pt(C2H4)OTf (4) (PyPyr = 3,5-diphenyl-2-(2-pyridyl)pyrrolide) were treated with 1 equiv of LiN(SiMe3)2, LiNiPr2, and LiNH(o-xylyl) to produce the platinum complexes (PyPyr)PtH[η2-CH2═CHN(SiMe3)2] (5), (PyPyr)Pt[κ2C,N-(CH2CH2NiPr2)] (6), and (PyPyr)Pt{κ2C,N-[CH2CH2NH(o-xylyl)]} (7), respectively. X-ray crystallography reveals that 7 adopts a square-planar geometry at the platinum center and the azaplatinacyclobutane ring displays a puckering of the β-carbon out of planarity by 0.270 Å. Thermolysis of 5 and 7 at 60 °C for 16 h releases the vinylamines (CH2═CH)N(SiMe3)2 and (CH2═CH)NH(o-xylyl), respectively. Heating 5 and 7 under 1 atm of H2 at 60 °C releases the ethylamines EtN(SiMe3)2 and EtNH(o-xylyl), respectively. Addition of PiPr3 to 7 produces (PyPyr)Pt(PiPr3)[CH2CH2NH(o-xylyl)] (8) in 95% yield, while additions of 1 equiv of a Lewis base (L) to 1 result in displacement of ethylene to give (PyPyr)Pt(L)Cl (L = NEt3 (9), NH2Ph (10), PiPr3 (11)). The amido complex (PyPyr)Pt(PiPr3)[NH(o-xylyl)] (12) results from treament of 11 with LiNH(o-xylyl), and 12 does not undergo ethylene insertion into the Pt−N bond under 1 atm of C2H4 at 120 °C over 3 days. Addition of 1 equiv of LiNH(o-xylyl) to (PyPyr)Pt(SMe2)Cl (2) produces the μ-amido-bridged dimer [(PyPyr)Pt(μ-NH(o-xylyl))]2 (13), and treatment of 13 with 2 equiv of iPr3P produces 12. These reactivity studies are consistent with a mechanism for the formation of 5−7 involving nucleophilic attack of an amide onto coordinated olefin.
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Abstract Reported herein is the iridium‐catalyzed regio‐ and enantioselective allylic substitution reactions of unstabilized silyl dienolates derived from dioxinones. Asymmetric allylic substitution of a variety of allylic trichloroethyl carbonates with these silyl dienolates gave γ‐allylated products selectively in 60–84 % yield and 90–98 % ee .