26 research outputs found

    Exile and Montage: Josep Renaus Reckoning with Community and Self

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    This paper examines Spanish photomontagist, Josep Renaus artistic progression through two exiles (the first in Mexico and the second in East Germany) as an example in which an individual defines his cultural identity first in the context of community, a collective leftist-socialist identity, and then as Stuart Hall points out in terms of \u27difference.\u27 When history reveals to Renau his separation from the community, he has no choice but to find himself in an expression of difference — not from the home he makes for himself in Mexico so much as from the neighbor he must criticize in order to earn his space among Mexican artists. Ironically Renau cannot express that difference until he leaves Mexico, and reintegrates back into a community, at least with ties to the one he initially lost in a communist European setting.\u2

    The ketimide ligand is not just an inert spectator: heteroallene insertion reactivity of an actinide-ketimide linkage in a thorium carbene amide ketimide complex

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    The ketimide anion R2C[DOUBLE BOND]N− is an important class of chemically robust ligand that binds strongly to metal ions and is considered ideal for supporting reactive metal fragments due to its inert spectator nature; this contrasts with R2N− amides that exhibit a wide range of reactivities. Here, we report the synthesis and characterization of a rare example of an actinide ketimide complex [Th(BIPMTMS){N(SiMe3)2}(N[DOUBLE BOND]CPh2)] [2, BIPMTMS=C(PPh2NSiMe3)2]. Complex 2 contains Th[DOUBLE BOND]Ccarbene, Th[BOND]Namide and Th[BOND]Nketimide linkages, thereby presenting the opportunity to probe the preferential reactivity of these linkages. Importantly, reactivity studies of 2 with unsaturated substrates shows that insertion reactions occur preferentially at the Th[BOND]Nketimide bond rather than at the Th[DOUBLE BOND]Ccarbene or Th[BOND]Namide bonds. This overturns the established view that metal-ketimide linkages are purely inert spectators

    Mixed sandwich imido complexes of Uranium(V) and Uranium(IV): Synthesis, structure and redox behaviour

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    The mixed sandwich U(III) complex {U[η ^8 -C8H6(1,4-Si( iPr)3)2](Cp*)(THF)} reacts with the organic azides RN3 (R = SiMe3, 1-Ad, BMes2) to afford the corresponding, structurally characterised U(V) imido complexes {U[η ^8 -C8H6(1,4-Si( iPr)3)2](Cp*)(NR)}. In the case of R=SiMe3, the reducing power of the U(III) complex leads to reductive coupling as a parallel minor reaction pathway, forming R-R and the U(IV) azide-bridged complex{[U]}2(”-N3)2, along with the expected [U]=NR complex. All three [U] =NR complexes show a quasi-reversible one electron reduction between -1.6 to -1.75 V, and for R= SiMe3, chemical reduction using K/Hg affords the anionic U(IV) complex K+ {U[η ^8 -C8H6(1,4-Si( iPr)3)2](Cp*)=NSiMe3} - . The molecular structure of the latter shows an extended structure in the solid state in which the K counter cations are successively sandwiched between the Cp* ligand of one [U] anion and the COTtips2 ligand of the next

    Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions

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    The reactivity of terminal uranium(V/VI) nitrides with CE2 (E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(TrenTIPS)(N)][K(B15C5)2] (1, TrenTIPS=N(CH2CH2NSiiPr3)3; B15C5=benzo-15-crown-5) reacts with CO2 to give [U(TrenTIPS)(O)(NCO)][K(B15C5)2] (3), whereas the uranium(VI) nitride [U(TrenTIPS)(N)] (2) reacts with CO2 to give isolable [U(TrenTIPS)(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(TrenTIPS)(O)] (5) with concomitant formation of N2 and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS2 to give [U(TrenTIPS)(Îș2-CS3)][K(B15C5)2] (6), 2, and [K(B15C5)2][NCS] (7), whereas 2 reacts with CS2 to give [U(TrenTIPS)(NCS)] (8) and “S”, with the latter trapped as Ph3PS. Calculated reaction profiles reveal outer-sphere reactivity for uranium(V) but inner-sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE2 follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common one-electron reactions and a less-common two-electron redox event. Caution, we suggest, is warranted when utilising CS2 as a reactivity surrogate for CO2

    The Renaissance of Non-Aqueous Uranium Chemistry

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    General Villa and General Pershing: Digitizing the Photographic Record of their Border Pursuits. Power Point presentation only.

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    Power point presentation on a collection of postcards depicting the 1916 Punitive Expedition into Mexico. Postcards includes scenes of battlefields, military parades, soldiers in barracks, and some tourist postcards
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