Le décret d’émancipation imaginaire : monarchisme et esclavage en Amérique du Nord et dans la Caraïbe au temps des révolutions

Dans les Amériques de l’époque coloniale, et notamment dans la Caraïbe, les esclaves sont souvent influencés par la rumeur annonçant qu’un roi a décrété leur émancipation, mais que les propriétaires d’esclaves ou les autorités coloniales refusent de le publier. Au nom de ces lois imaginaires, de nombreuses révoltes d’esclaves se déclenchent du milieu du xviie siècle jusqu’au cœur du xixe, avec un apogée dans les années qui suivent la Révolution française.In the colonial Americas and especially in the Caribbean, black slaves were often influenced by the rumor that a king had decreed their emancipation. The refusal of slaveowners and colonial authorities to honor this imaginary decree set off revolts from the mid-seventeenth to the mid-nineteenth century, their number peaking after the outbreak of the French Revolution

Interrupted Continuities: Transatlantic Relations during and after the Age of Revolutions (1775–1824)

This essay reviews the following works: Connections after Colonialism: Europe and Latin America in the 1820s. Edited by Matthew Brown and Gabriel Paquette. Tuscaloosa: University of Alabama Press, 2013. Pp. vii + 328. $54.95 cloth. ISBN: 9780817317768. Frontiers of Possession: Spain and Portugal in Europe and the Americas. By Tamar Herzog. Cambridge, MA: Harvard University Press, 2015. Pp. i + 377.$35.00 cloth. ISBN: 9780674735385. Imperial Portugal in the Age of Atlantic Revolutions: The Luso-Brazilian World, c. 1770–1850. By Gabriel Paquette. New York: Cambridge University Press, 2013. Pp. vi + 445. $140.00 cloth. ISBN: 9781107028975. Revolutions without Borders: The Call to Liberty in the Atlantic World. By Janet Polasky. New Haven: Yale University Press, 2016. Pp. 392.$25.00 paper. ISBN: 9780300219845. Crisis in an Atlantic Empire: Spain and New Spain, 1808–1810. By Barbara H. Stein and Stanley J. Stein. Baltimore: John Hopkins University Press, 2014. Pp. ix + 773. $89.95 cloth. ISBN: 9781421414249. Empire’s End: Transnational Connections in the Hispanic World. Edited by Akiko Tsuchiya and William G. Acree Jr. Nashville: Vanderbilt University Press, 2016. Pp. ix + 223.$34.95 cloth. ISBN: 9780826520777

La República Holandesa y su posición en el contexto colonial americano después de 1713

During the War of Spanish Succession, the Dutch Republic fought alongside the Austrians and their allies against the Bourbon party. Still, and in spite of its alliance with England, the treaties of Utrecht did not leave the Dutch Republic in a good position. In this article, these treaties’ consequences for the commercial and colonial Dutch expansion in the Atlantic world are analyzed.Durante la guerra de Sucesión española, la República Holandesa luchó junto al bloque aliado austracista contra la opción borbónica. Sin embargo, y a pesar de su alianza con Inglaterra, la República Holandesa no salió bien restablecida de los tratados de Utrecht. En este artículo se analizarán las consecuencias que estos tratados tuvieron para la expansión comercial y colonial de Holanda en el Atlántico

Synthesis, Structure, and Properties of Compounds in the NaHSO_4−CsHSO_4 System. 1. Crystal Structures of Cs_2Na(HSO_4)_3 and CsNa_2(HSO_4_)3

Exploratory synthesis in the NaHSO₄-CsHSO₄ system, aimed at discovering novel proton conducting solids, resulted in the new compounds CsNa₂(HSO₄)₃ and Cs₂Na(HSO₄)₃. Single-crystal X-ray diffraction (performed at room temperature) revealed CsNa₂(HSO₄)₃ to crystallize in the cubic space group P2₁3 with lattice parameters a=10.568(2)Å and Z=4, whereas CS2Na(HSO₄)₃, studied by both single-crystal neutron and X-ray methods, crystallizes in the hexagonal space group P6₃/m. The latter compound has lattice parameters a=8.5712(17) and c=9.980(2)Å, and Z=2. The unit cell volumes are 1180.4(4) and 634.9(2)ų, respectively, giving calculated densities of 2.645 and 3.304 mg m⁻³. Refinement using all observed reflections yielded a weighted residual, R-w(F²), of 0.0515 based on F² X-ray values for CsNa₂(HSO₄)₃. For Cs₂Na(HSO₄)₃ the analogous X-ray and neutron values were 0.0483 and 0.1715, respectively. Both structures contain a single, crystallographically distinct, asymmetric hydrogen bond (as confirmed by NMR investigations) and unique, three-membered (HSO₄)₃ rings. The geometric match between the NaO₆ octahedra and the rings suggests the sodium polyhedra may serve to template the (HSO₄)₃ unit. In CsNa₂(HSO₄)₃ the rings form a distorted cubic close-packed array. The Cs atoms are located within the "octahedral" sites of this array, and the Na atoms, within the "tetrahedral" sites. The rings in CS₂Na(HSO₄)₃ are linked together by NaO6 octahedra to form infinite Na(HSO₄)₃ chains that extend along 001. The hexagonal compound exhibits disorder about the sulfate tetrahedron that suggests a P6₃/m → P6 phase transition may occur upon cooling

Cerium(III) and cerium(IV) nitrate complexes of trialkylphosphine oxides

Abstract The reactions of ammonium cerium(IV) nitrate, (NH4)2Ce(NO3)6 (CAN) with trialkylphosphine oxides, R3PO (R= Et, iPropyl, nBu3, iBu3PO, tBu3PO, Cy3PO (Cy = cyclohexyl) and Oct3PO (Oct = n-octyl)) have been investigated by 31-P NMR spectroscopy in a variety of conditions. Reactions with acetone solutions of excess of CAN and R3PO and of solid CAN with chloroform solutions of R3PO and aqueous solutions of CAN with chloroform solutions of R3PO led to the observation of Ce(NO3)4(R3PO)2. 31-P NMR spectroscopy and conductimetric titration of acetone solutions of CAN with R3PO confirm the initial reactions is the formation of Ce(NO3)4(R3PO)2 (R = Et, Bu, Cy, Oct) followed by a slower reaction to form the ionic [Ce(NO3)3(R3PO)3][NO3]. The isolation of pure cop-lexes has not proved possible in most cases but crystals suitable for x-ray analysis were extracted in some instances. The structures of the Ce(IV) complexes [Ce(NO3)4(Cy3PO)2] and [Ce(NO3)3(Et3PO)3][NO3] and the related Ce(III) complexes [Ce(NO3)3(Cy3PO)3] and [Ce(NO3)3(H2O)3(Et3PO)] are reported

Intermolecular Interactions in Molecular Crystals and Their Effect on Thermally Activated Delayed Fluorescence of Helicene-Based Emitters

Here, we discuss the influence of the crystal structure on the photophysical properties of two new TADF emitters containing a non-planar helical moiety. The presence of solvent in the crystal lattice of a diaza[5]helicene-based compound alters molecular packing significantly and suppresses aggregation. This results in more intense TADF emission and an increase in PLQY. Solution-processed OLED devices gave a maximum external quantum efficiency of 7.1%

Lanthanide tri- and tetrathionates and their complexes with triphenylphosphine oxide

Lanthanide tri- and tetrathionate containing species have been prepared in solution by the reaction of potassium tri- and tetrathionate with lanthanide perchlorates. Unstable solid materials from these reactions have been examined by infrared spectroscopy and electrospray mass spectrometry (ESI MS). There was evidence of the formation of S3O62- and S4O62- coordination to lanthanide ions, but it was not possible to produce material suitable for single crystal x-ray studies. The reaction of ethanol solutions from Ln(ClO4)3 / K2SnO6 (n = 3,4) with triphenylphosphine oxide yielded crystalline materials which have been characterised by infrared spectroscopy, electrospray mass spectrometry, elemental analysis and single crystal X-ray diffraction. The trithionate complexes [Ln(S3O6)(Ph3PO)4]ClO4.3H2O (Ln = Nd, Tb) have been isolated. The tetrathionate / Ph3PO reaction gave rise to significant disproportionation giving a small quantity of [Nd(S4O6)(Ph3PO)4(H2O)]ClO4, a different isomer of [Nd(S3O6)(Ph3PO)4H2O]ClO4, neodymium sulfate and elemental sulfur. The crystal structures of the two isomers of [Nd(S3O6)(Ph3PO)4H2O]ClO4 and that of [Nd(S4O6)(Ph3PO)4H2O]ClO4 are reported. The structure of [Er(H2O)5(Ph3PO)2].5Ph3PO.3[ClO-4], formed during the attempted preparation of erbium trithionate complexes, is also described

The asymmetric aza-silyl-prins reaction: Synthesis of enantiopure piperidines

The design and development of the first asymmetric aza-silyl-Prins reaction is reported, giving rise to valuable and diverse piperidines and pipecolic acid derivatives in both high yields and as single enantiomers. The creation of a novel chiral auxiliary-homoallylic amine for the aza-silyl-Prins reaction is essential to its success

Hydride Transfer to Gold: Yes or No? Exploring the Unexpected Versatility of Au···H‐M Bonding in Heterobimetallic Dihydrides

The potential for coordination and H-transfer from Cp2MH2 (M = Zr, W) to gold(I) and gold(III) complexes was explored in a combined experimental and computational study. [(L)Au]+ cations react with Cp2WH2 giving [(L)Au(κ2-H2WCp2)]+ (L = IPr ( 1 ), cyclic (alkyl)(amino)carbene ( 2) , or phosphines PPh3 (3) and Dalphos-Me (4) [IPr = 1,3-bis(diisopropylphenyl)imidazolylidene; Dalphos-Me = di(1-adamantyl)-2-(dimethylamino)phenyl-phosphine], while [Au(DMAP)2]+ (DMAP = p-dimethylaminopyridine) affords the C2-symmetric [Au(κ-H2WCp2)2]+ (5) . The Dalphos complex 4 can be protonated to give the bicationic adduct 4H , showing Au(I)…H+-N hydrogen bonding. The gold(III) Lewis acid [(C^N-CH)Au(C6F5)(OEt2)]+ binds Cp2WH2 to give an Au-H-W σ-complex. By contrast, the pincer species [(C^N^C)Au]+ adds Cp2WH2 by a purely dative W→Au bond, without Au···H interaction. The biphenyl-based chelate [(C^C)Au]+ forms [(C^C)Au(µH)2WCp2]+, with two 2-electron-3-centre W-H…Au interactions and practically no Au-W donor acceptor contribution. In all these complexes strong but polarised W-H bonds are maintained, without H-transfer to gold. On the other hand, the reactions of Cp2ZrH2 with gold complexes led in all cases to rapid H-transfer and formation of gold hydrides. Relativistic DFT calculations were used to rationalize the striking reactivity and bonding differences in these heterobimetallic hydride complexes along with an analysis of their characteristic NMR parameters and UV-Vis absorption properties