127 research outputs found
Bouncing back from failure: Entrepreneurial resilience and the internationalization of subsequent ventures created by serial entrepreneurs
This paper examines the impact over international propensity of past negative entrepreneurial experience for those who re-enter into entrepreneurial activity; referred to as resilient serial entrepreneurs. We first hypothesize on the effects over entrepreneurial re-entry that such negative past experience may have and highlight the link between the past entrepreneurial experience of resilient entrepreneurs and their subsequent propensity towards international markets. Building on insights from the generative experiential learning process of entrepreneurial activity and from cognition theories, we propose that resilient entrepreneurs who re-enter business despite having faced negative entrepreneurial experiences in the past benefit from enriched cognitive schemas leading them to greater export propensity. The proposed hypotheses are tested on a unique sample drawn from a Spanish adult population survey. Results from the sequential deductive triangulation analysis (QUAN -> qual) reveal that practical experience is an essential prerequisite for entrepreneurial learning, and that the resilience of those with negative entrepreneurial experience induces the generative entrepreneurial learning especially suitable for subsequent internationally oriented ventures.Peer ReviewedPreprin
Kinetic and DFT Studies on the Mechanism of C−S Bond Formation by Alkyne Addition to the [Mo3S4(H2O)9]4+ Cluster
Reaction of [Mo3(μ3-S)(μ-S)3] clusters with alkynes usually leads to formation of two C−S bonds between the
alkyne and two of the bridging sulfides. The resulting compounds contain a bridging alkenedithiolate ligand, and the metal centers appear to play a passive role despite reactions at those sites being well illustrated for this kind of cluster. A detailed study including kinetic measurements and DFT calculations has been carried out to understand the mechanism of reaction of the [Mo3(μ3-S)(μ-S)3(H2O)9]4+ (1) cluster with two different alkynes, 2-butyne-1,4-diol and acetylenedicarboxylic acid. Stoppedflow experiments indicate that the reaction involves the appearance in a single kinetic step of a band at 855 or 875 nm, depending on the alkyne used, a position typical of clusters with two C−S bonds. The effects of the concentrations of the reagents, the acidity, and the reaction medium on the rate of reaction have been analyzed. DFT and TD-DFT calculations provide information on the nature of the product formed, its electronic spectrum and the energy profile for the reaction. The structure of the transition state indicates that the alkyne approaches the cluster in a lateral way and both C−S bonds are formed simultaneously
Orientação empreendedora e competências de marketing no desempenho organizacional: um estudo em empresas de base tecnológica
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Unexpected formation of the novel mixed mu-oxo, mu-sulfido, bis(mu-thiolato) compound [Mo(IV)(2)(Cp-2(mu-O)(mu-S)(mu-SMe)(2)]
cited By 7International audienceA novel example of C-S bond cleavage in a dimolybdenum derivative leads to the formation of the quadruply bridged compound [Mo(IV)2Cp2(μ-O)(μ-S)(μ-SMe)2]. This μ-oxo species is formed by reaction of the chloro-bridged complex [Mo(III)2Cp2(μ-Cl)(μ-SMe)3] with PhCCLi and subsequent hydration at the dimolybdenum site. The Mo-Mo bond length of 2.4900(3)Å in [Mo2Cp2(μ-O)(μ-S)(μ-SMe)2] is unusually short. © 2001 Elsevier Science B.V
Reaction of BH4- with {Mo2Cp2(mu-SMe)(n)} species to give tetrahydroborato, hydrido or dimetallaborane compounds: control of product by ancillary ligands
cited By 28International audienceThe reaction of mono- or dichloro-dimolybdenum(m) complexes [Mo 2Cp2(μ-SMe)2(μ-Cl)(μ-Y)] (Cp=η5-C5H5; 1, Y = SMe; 2, Y = PPh 2; 3, Y = Cl) with NaBH4, at room temperature gave in high yields tetrahydroborato (8), hydrido (9) or metallaborane (12) complexes depending on the ancillary ligands. The correct formulation of derivatives 8 and 12 has been unambigously determined by X-ray diffraction methods. That of the hydrido compound 9 has been established in solution by NMR analysis and confirmed by an X-ray study of the μ-azavinylidene derivative [Mo 2Cp2(μ-SMe)2(μ-PPh2)(μ-N= CHMe)] (10) obtained from the insertion of acetonitrile into the Mo-H bond of 9. Reaction of NaBH4, with nitrile derivatives, [Mo2Cp 2(μ-SMe)4-n(CH3CN)2n] n+ (5, n= 1; 6 =2), afforded the tetrahydroborato compound 8, together with a μ-azavinylidene species [Mo2Cp2(μ- SMe)3(μ-N=CHMe)] (14), when n= 1, and the metallaborane complex 12, together with a mixed borohydrato-azavinylidene derivative [Mo 2Cp2(μ-SMe)2(μ-BH4)(μ-N= CHMe)] (13), when n=2. The molecular structures of these complexes have been confirmed by X-ray analysis. Preparations of some of the starting complexes (3 and 4) are also described, as are the molecular structures of the precursors [Mo2Cp2(μ-SMe)2(μ-X)-(μ-Y)] (1, X/Y = Cl/SMe; 2, X/Y = Cl/PPh2; 4, X/Y = SMe/PPh2)
cis- and trans-bis(1-phenyl-2,3,4,5-tetramethylphosphole)tetracarbonylmolybdenum(0), [Mo(CO)(4)(tmpPh)(2)]. Syntheses and structures
cited By 7International audience1-Phenyl-2,3,4,5-tetramethylphosphole reacts with [Mo(CO)6] to give the mono- and bis(phosphole) complexes [Mo(CO)5L] and cis- and trans-[Mo(CO)4L2], where L=C4Me4PPh (tmpPh). The new complexes have been characterised by spectroscopic methods, supplemented by single-crystal X-ray analyses in the case of the bis(phosphole) isomers. The isomeric bis-tmpPh complexes show little evidence of the overcrowding which is thought to lengthen bonds and distort the metal coordination in the corresponding bis-PPh3 and bis-PCy3 isomers. The structural basis for the greater stability of the trans isomers is briefly considered: the cis→trans isomerisation typically involves little change in the mean Mo-CO distance, whereas there is a marked shortening of the Mo-P bonds. © 2001 Elsevier Science B.V
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