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Aerobic alcohol oxidation catalyzed by the newly synthesized dimeric [(neocuproine)Pd(µ-OAc)] 2 -(OTf) 2 (1; neocuproine ) 2,9-dimethyl-1,10-phenanthroline) proceeds under exceptionally mild conditions (room temperature, ambient air) compared to those required for the previously reported monomeric diacetate analogue (neocuproine)Pd(OAc) 2 (2) and the monomeric ditriflate analogue (neocuproine)Pd-(MeCN) 2 (OTf) 2 (3). An unprecedented initial turnover frequency (TOF i ) for such mild conditions (78 (Pd atom) -1 h -1 ) is observed with catalyst 1; however, competitive oxidation of a methyl group on the ligand to a carboxylate group results in catalyst inactivation. During the study of 1, we isolated for the first time [(neocuproine)Pd(µ-OH)] 2 (OTf) 2 (4), a possible intermediate in the catalytic cycle, and we report its crystal structure and catalytic activity herein.

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The regio- and chemoselective oxidation of unprotected vicinal polyols with [(neocuproine)Pd(OAc)]2(OTf)2 (1) (neocuproine = 2,9-dimethyl-1,10-phenanthroline) occurs readily under mild reaction conditions to generate α-hydroxy ketones. The oxidation of vicinal diols is both faster and more selective than the oxidation of primary and secondary alcohols; vicinal 1,2-diols are oxidized selectively to hydroxy ketones, whereas primary alcohols are oxidized in preference to secondary alcohols. Oxidative lactonization of 1,5-diols yields cyclic lactones. Catalyst loadings as low as 0.12 mol % in oxidation reactions on a 10 g scale can be used. The exquisite selectivity of this catalyst system is evident in the chemoselective and stereospecific oxidation of the polyol (S,S)-1,2,3,4-tetrahydroxybutane [(S,S)-threitol] to (S)-erythrulose. Mechanistic, kinetic, and theoretical studies revealed that the rate laws for the oxidation of primary and secondary alcohols differ from those of diols. Density functional theory calculations support the conclusion that β-hydride elimination to give hydroxy ketones is product-determining for the oxidation of vicinal diols, whereas for primary and secondary alcohols, pre-equilibria favoring primary alkoxides are product-determining. In situ desorption electrospray ionization mass spectrometry (DESI-MS) revealed several key intermediates in the proposed catalytic cycle.

The retroarc fold-and-thrust belt of the Central Andes exhibits major along-strike variations in its pre-Cenozoic tectonic confi guration. These variations have been proposed to explain the considerable southward decrease in the observed magnitude of Cenozoic shortening. Regional mapping, a cross section, and U-Pb and (U-Th)/He age dating of apatite and zircon presented here build upon the preexisting geological framework for the region. At the latitude of the regional transect (24-25°S), results demonstrate that the thrust belt propagated in an overall eastward direction in three distinct pulses during Cenozoic time. Each eastward jump in the deformation front was apparently followed by local westward deformation migration, likely refl ecting a subcritically tapered orogenic wedge. The fi rst eastward jump was at ca. 40 Ma, when deformation and exhumation were restricted to the western margin of the Eastern Cordillera and eastern margin of the Puna Plateau. At 12-10 Ma, the thrust front jumped ~75 km toward the east to bypass the central portion of a horst block of the Cretaceous Salta rift system, followed by initiation of new faults in a subsystem that propagated toward the west into this preexisting structural high. During Pliocene time, deformation again migrated >100 km eastward to a Cretaceous synrift depocenter in the Santa Bárbara Ranges. The sporadic foreland-ward propagation documented here may be common in basement-involved thrust systems where inherited weaknesses due to previous crustal deformation are preferentially reactivated during later shortening. The minimum estimate for the magnitude of shortening at this latitude is ~142 km, which is moderate in magnitude compared to the 250-350 km of shortening accommodated in the retroarc thrust belt of southern Bolivia to the north. This work supports previous hypotheses that the magnitude of shortening decreases signifi cantly along strike away from a maximum in southern Bolivia, largely as a result of the distribution of pre-Cenozoic basins that are able to accommodate a large magnitude of thinskinned shortening. A major implication is that variations in the pre-orogenic upper-crustal architecture can infl uence the behavior of the continental lithosphere during later orogenesis, a result that challenges geodynamic models that neglect upper-plate heterogeneities.

Conflicting models of Rodinian rifting have been proposed to explain the recognized variation in the Neoproterozoic and early Cambrian tectonostratigraphic architecture of the western Laurentian margin. However, discrimination among rift models is hampered by limited exposure and metamorphism of the rocks. Southeastern Idaho preserves more than 6 km of Neoproterozoic and Cambrian strata. In contrast, along the inferred continuation of the margin in east central Idaho, correlative rocks are missing across the Lemhi arch. Our field mapping and U‐Pb dating studies, located approximately 50 km west of the Lemhi arch unconformity, focused on a succession of regionally extensive rocks that were previously assigned an Ordovician age. We show that ~1.5 km of strata here overlies a ~667 Ma reworked felsic tuff and was intruded by a 601 ± 27 Ma gabbro sill; we thus redesignate these rocks as Cryogenian and Ediacaran in age. These rocks are overlain by a ~1 km thick Ediacaran to middle Cambrian quartzite. Middle Ordovician quartzites overlie these middle Cambrian strata, indicating that though Neoproterozoic and lower Cambrian rocks are present west of the Lemhi arch, upper Cambrian and Lower Ordovician rocks are thin or absent. Comparison of this redesignated section to the closest correlative sections suggests an initial stage of symmetric rifting followed by later asymmetric rifting. We suggest that prerifting ~1,370 Ma magmatism within the Belt basin produced lithospheric rigidity that influenced the final stage of rifting and produced heterogeneity in the geometries of structural domains similar to those documented in other well‐defined, modern rift margins.

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The Laramide province is characterized by foreland basin partitioning through the growth of basement arches. Although variable along the western U.S. margin, the general consensus is initiation of this structural style by the early Campanian (~80 Ma). This has been linked to flat-slab subduction beneath western North America, but the extent and cause for a flat slab remain debated, invoking the need for better constraints on the regional variations in timing of Laramide deformation. We present new conglomerate clast composition, sandstone petrographic, and detrital zircon U-Pb geochronologic data from the Upper Cretaceous Beaverhead Group in southwestern Montana that suggest a pre-Campanian history of basement-involved deformation. During the early stages of deposition (~88-83 Ma), two separate depositional systems derived sediment from the Lemhi subbasin and distal thrust sheets to the west as well as Paleozoic strata eroding off the exhuming Blacktail-Snowcrest arch to the east. Our data provide the first conclusive evidence for the longitudinal transport of gravel via Cordilleran paleorivers connecting sediment sources in east central Idaho to depocenters in southwestern Montana and northwestern Wyoming. Furthermore, erosion of Paleozoic strata by this time requires that the Blacktail-Snowcrest arch was exhuming prior to~88 Ma in order to remove the Mesozoic overburden. Later (~73-66 Ma) sediment flux was entirely from the foreland-propagating fold-thrust belt to the west. These results suggest that Laramide-style deformation in southwestern Montana preceded initiation elsewhere along the margin, requiring revision of existing models for Laramide tectonism.