10,264 research outputs found

    Functional Constitutivism’s Misunderstood Resources: A Limited Defense of Smith’s Constitutivism

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    In recent work, Michael Smith argues that particular desires are constitutive of ideal agency and draws on his dispositional account of reasons to establish the normative significance of those desires. In a sustained critique, Michael Bukowski objects that Smith’s recent arguments that particular desires are constitutive of ideal agency rely on indefensible premises and his dispositional account of reasons is unable to establish the normative significance of such desires. On the contrary, I argue not only that Smith has the resources to respond to these objections but also that the form of Smith’s constitutivist explanation has unappreciated explanatory strengths

    Constitutivism without Normative Thresholds

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    Constitutivist accounts in metaethics explain the normative standards in a domain by appealing to the constitutive features of its members. The success of these accounts turns on whether they can explain the connection between normative standards and the nature of individuals they authoritatively govern. Many such explanations presuppose that any member of a norm-governed kind must minimally satisfy the norms governing its kind. I call this the Threshold Commitment, and argue that constitutivists should reject it. First, it requires constitutivists to restrict the scope of their explanatory ambitions, because it is not plausibly true of social kinds. Second, despite the frequent reliance on physical artifacts in constitutivists’ illustrations of the Threshold Commitment, it counter-intuitively entails that physical artifacts can cease to exist without being physically destroyed. Third, it misconstrues the normative force of authoritative norms on very defective kind-members because it locates this force not in the norm, but in the threat of non-existence. Fortunately, constitutivism can be decoupled from the Threshold Commitment, and I close by sketching a promising alternative account

    ISOMETRY OF EGG SIZE IN A TEXAS POPULATION OF THE TURTLE STERNOTHERUS ODORATUS THAT EXHIBITS A NEARLY FIXED CLUTCH SIZE

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    In evaluating optimal egg-size theory and the effects of anatomical constraints on egg size in turtles, pivotal questions concern the significance of the relationship of egg size to female body size and whether the relationship is isometric or hypoallometric. In a central Texas population of the kinosternid turtle Sternotherus odoratus in which clutch size of a sample of turtles was nearly fixed (seven of eight females had two eggs while the largest female had three eggs), there was an isometric increase in egg width with body size among the females with two-egg clutches and significantly reduced egg width in the largest female’s three-egg clutch. Allometric analyses of populations that exhibit little variation in clutch size, as well as analysis of modal clutch sizes in populations with more variable clutch sizes, both have the potential to further illuminate the competing demands of increasing egg size vs. increasing clutch size as females grow larger, enabling them to optimize their reproductive output as it increases with body size

    Synthesis and Characterization of platinum – selenium Derivatives: X-ray Structure of \u3cem\u3etrans\u3c/em\u3e-Pt(Pet\u3csub\u3e3\u3c/sub\u3e)\u3csub\u3e2\u3c/sub\u3e(SePh)\u3csub\u3e2\u3c/sub\u3e

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    The crystal structure of trans-[((bis)triethylphosphine)(bis(phenylselenato))platinum (II)] has been determined by single crystal X-ray diffraction. Crystallization occurs in the triclinic space group P-1 (No. 2) with a = 8.9964(2) Å, b = 11.5103(2) Å, c = 14.9335(3) Å; α = 85.8750(10)°, β = 72.5350(10)°, γ = 68.4450(10)°. Details of the structure and spectroscopic results are presented and discussed and comparisons are made with related square planar platinum (II) structures

    Copper-Catalyzed Arylation of 1\u3cem\u3eH\u3c/em\u3e-Perfluoroalkanes

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    A general method has been developed for arylation of readily available 1H-perfluoroalkanes. The method employs aryl iodide and 1H-perfluoroalkane reagents, DMPU solvent, TMP2Zn base, and a copper chloride/phenanthroline catalyst. Preliminary mechanistic studies are reported

    Bimetallic Complexes Supported by a Redox-Active Ligand with Fused Pincer-Type Coordination Sites

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    The remarkable chemistry of mononuclear complexes featuring tridentate, meridionally chelating “pincer” ligands has stimulated the development of ligand frameworks containing multiple pincer sites. Here, the coordination chemistry of a novel pentadentate ligand (LN3O2) that provides two closely spaced NNO pincer-type compartments fused together at a central diarylamido unit is described. The trianionic LN3O2 chelate supports homobimetallic structures in which each M(II) ion (M = Co, Cu, Zn) is bound in a meridional fashion by the bridging diarylamido N atom and O,N-donors of the salicyaldimine arms. The metal centers are also coordinated by a mono- or bidentate auxiliary ligand (Laux), resulting in complexes with the general form [M2(LN3O2)(Laux)2]+ (where Laux = 1-methyl-benzimidazole (1MeBI), 2,2′-bipyridine (bpy), 4,4′-dibromo-2,2′-bipyridine (bpyBr2), or (S)-2-(4-isopropyl-4,5-dihydrooxazolyl)pyridine (S-iPrOxPy)). The fused nature of the NNO pincer sites results in short metal–metal distances ranging from 2.70 Å for [Co2(LN3O2) (bpy)2]+ to 3.28 Å for [Zn2(LN3O2) (bpy)2]+, as revealed by X-ray crystallography. The complexes possess C2 symmetry due to the twisting of the aryl rings of the μ-NAr2 core; spectroscopic studies indicate that chiral Laux ligands, such as S-iPrOxPy, are capable of controlling the helical sense of the LN3O2 scaffold. Since the four- or five-coordinate M(II) centers are linked solely by the amido moiety, each features an open coordination site in the intermetallic region, allowing for the possibility of metal–metal cooperativity in small-molecule activation. Indeed, the dicobalt(II) complex [Co2(LN3O2) (bpyBr2)2]+ reacts with O2 to yield a dicobalt(III) species with a μ-1,2-peroxo ligand. The bpy-containing complexes exhibit rich electrochemical properties due to multiple metal- and ligand-based redox events across a wide (3.0 V) potential window. Using electron paramagnetic resonance (EPR) spectroscopy and density functional theory (DFT), it was determined that one-electron oxidation of [Co2(LN3O2) (bpy)2]+ results in formation of a S = 1/2 species with a LN3O2-based radical coupled to low-spin Co(II) centers

    Electron Transfer Prompted Ejection of a Tightly Bound K\u3csup\u3e+\u3c/sup\u3e from the Ethereal Cavity of a Hexaarylbenzene-Based Receptor

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    Synthesis of a pair of rotamers (9u/9s) of a hexaarylbenzene derivative containing six (cofacially arranged) electroactive 2,5-dimethoxytolyl groups is described. The toroidal electronic stabilization due to the circular arrangement of aryl groups in 9u/9s leads to the observation of multiple (reversible) oxidation waves and lowering of their Eox1 by ∼250 mV relative to model compounds. The binding of K+ to symmetrical rotamer 9s was monitored by an electrochemical method and further confirmed by X-ray crystallography

    A Polyaromatic Receptor with an Ethereal Fence that Directs K\u3csup\u3e+\u3c/sup\u3e for Effective Cation−π Interaction

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    We have designed and synthesized a HAB-based receptor with six ethereal oxygens on one face of the central benzene ring by a trimerization of a diarylacetylene in which the ethereal oxygens are tied together with a tetramethylene bridge. This unique amphiphilic receptor allows an efficient binding of a single potassium cation by a synergistic interaction with the polar ethereal fence and with the central benzene ring via cation−π interaction. Furthermore, the ready accessibility of this unique receptor with a bipolar binding pocket will allow the exploration of its usage for developing efficient sensing devices for various metal cations

    The Charge-Transfer Motif in Crystal Engineering. Self-Assembly of Acentric (Diamondoid) Networks from Halide Salts and Carbon Tetrabromide as Electron-Donor/Acceptor Synthons

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    Unusual strength and directionality for the charge-transfer motif (established in solution) are shown to carry over into the solid state by the facile synthesis of a series of robust crystals of the [1:1] donor/acceptor complexes of carbon tetrabromide with the electron-rich halide anions (chloride, bromide, and iodide). X-ray crystallographic analyses identify the consistent formation of diamondoid networks, the dimensionality of which is dictated by the size of the tetraalkylammonium counterion. For the tetraethylammonium bromide/carbon tetrabromide dyad, the three-dimensional (diamondoid) network consists of donor (bromide) and acceptor (CBr4) nodes alternately populated to result in the effective annihilation of centers of symmetry in agreement with the sphaleroid structural subclass. Such inherently acentric networks exhibit intensive nonlinear optical properties in which the second harmonics generation in the extended charge-transfer system is augmented by the effective electronic (HOMO−LUMO) coupling between contiguous CBr4/halide centers
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