The reductive activation of CO2 across a Ti═Ti double bond: synthetic, structural, and mechanistic studies

[Image: see text] The reactivity of the bis(pentalene)dititanium double-sandwich compound Ti(2)Pn(†)(2) (1) (Pn(†) = 1,4-{Si(i)Pr(3)}(2)C(8)H(4)) with CO(2) is investigated in detail using spectroscopic, X-ray crystallographic, and computational studies. When the CO(2) reaction is performed at −78 °C, the 1:1 adduct 4 is formed, and low-temperature spectroscopic measurements are consistent with a CO(2) molecule bound symmetrically to the two Ti centers in a μ:η(2),η(2) binding mode, a structure also indicated by theory. Upon warming to room temperature the coordinated CO(2) is quantitatively reduced over a period of minutes to give the bis(oxo)-bridged dimer 2 and the dicarbonyl complex 3. In situ NMR studies indicated that this decomposition proceeds in a stepwise process via monooxo (5) and monocarbonyl (7) double-sandwich complexes, which have been independently synthesized and structurally characterized. 5 is thermally unstable with respect to a μ-O dimer in which the Ti–Ti bond has been cleaved and one pentalene ligand binds in an η(8) fashion to each of the formally Ti(III) centers. The molecular structure of 7 shows a “side-on” bound carbonyl ligand. Bonding of the double-sandwich species Ti(2)Pn(2) (Pn = C(8)H(6)) to other fragments has been investigated by density functional theory calculations and fragment analysis, providing insight into the CO(2) reaction pathway consistent with the experimentally observed intermediates. A key step in the proposed mechanism is disproportionation of a mono(oxo) di-Ti(III) species to yield di-Ti(II) and di-Ti(IV) products. 1 forms a structurally characterized, thermally stable CS(2) adduct 8 that shows symmetrical binding to the Ti(2) unit and supports the formulation of 4. The reaction of 1 with COS forms a thermally unstable complex 9 that undergoes scission to give mono(μ-S) mono(CO) species 10. Ph(3)PS is an effective sulfur transfer agent for 1, enabling the synthesis of mono(μ-S) complex 11 with a double-sandwich structure and bis(μ-S) dimer 12 in which the Ti–Ti bond has been cleaved

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

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)(κ2-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

Identification of the geographic origins of people buried in the cemetery of the Salesian Mission of Tierra del Fuego through the analyses of mtDNA and stable isotopes

Considering that the treatment of dead bodies constitutes an expression of the symbolic world, the objective of this work is to obtain greater knowledge about the regional geographic origins of the individuals buried in the post-European contact Salesian Mission “La Candelaria” of Tierra del Fuego. Historical data report that two groups of people made use of this cemetery: Native Americans from Southern Patagonia (indigenous) on one hand, and colonists and missionaries (non-indigenous) on the other hand. We used two new lines of evidence: mtDNA sequences and oxygen isotope data (δ18O), to identify these groups and assess whether the location of the individuals in the cemetery shows patterns that could be associated with group affiliation. Of the 26 individuals we tested, our results indicate that 85% of the individuals were local, i.e. Natives from Southern Patagonia and a 15% of the individuals came from outside this region (non-local). In the excavated sector of the cemetery, no trends were identified in the location and disposition of burials that could be associated with group affiliation. We found no differences in burial treatment that could indicate difference among individuals of European origin, migrants from nearby areas, and Natives from Southern Patagonia. While variability in the geographic origins of the people was expected considering the historical data, the fact that people with different geographic origins were buried together, without spatial separation within this section of the cemetery was not. The non-existence of spatial separation between indigenous and non-indigenous people may be related to the main objective of the missionary process: the evangelization of indigenous people. In this sense, all the individuals buried in the cemetery went through Christianization and their bodies were treated without observable differences between them.Fil: Motti, Josefina María Brenda. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ciencias Sociales. Grupo de Estudios Interdisciplinarios sobre Poblaciones Humanas de Patagonia Austral; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Winingear, S.. Arizona State University. School Of Human Evolution And Social Change; Estados UnidosFil: Valenzuela, Luciano Oscar. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ciencias Sociales. Grupo de Estudios Interdisciplinarios sobre Poblaciones Humanas de Patagonia Austral; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Nieves Colón, M. A.. Arizona State University. School Of Human Evolution And Social Change; Estados UnidosFil: Harkins, K. M.. Arizona State University. School Of Human Evolution And Social Change; Estados UnidosFil: Garcia Laborde, Pamela. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ciencias Sociales. Grupo de Estudios Interdisciplinarios sobre Poblaciones Humanas de Patagonia Austral; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Bravi, Claudio Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto Multidisciplinario de Biología Celular. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Instituto Multidisciplinario de Biología Celular. Universidad Nacional de La Plata. Instituto Multidisciplinario de Biología Celular; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo; ArgentinaFil: Guichon, Ricardo Anibal. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ciencias Sociales. Grupo de Estudios Interdisciplinarios sobre Poblaciones Humanas de Patagonia Austral; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Stone, A. C.. Arizona State University. School Of Human Evolution And Social Change. Center For Bioarchaeological Research.; Estados Unido

Hand skin reconstruction from skeletal landmarks

Many studies related to three-dimensional facial reconstruction have been previously reported. On the other hand, no extensive work has been found in the literature about hand reconstruction as an identification method. In this paper, the feasibility of virtual reconstruction of hand skin based on (1) its skeleton and (2) another hand skin and skeleton used as template was assessed. One cadaver hand and one volunteer's hand have been used. For the two hands, computer models of the bones and skin were obtained from computerized tomography. A customized software allowed locating spatial coordinates of bony anatomical landmarks on the models. From these landmarks, the spatial relationships between the models were determined and used to interpolate the missing hand skin. The volume of the interpolated skin was compared to the real skin obtained from medical imaging for validation. Results seem to indicate that such a method is of interest to give forensic investigators morphological clues related to an individual hand skin based on its skeleton. Further work is in progress to finalize the method.info:eu-repo/semantics/publishe