When Less Is Best: Female Brown-Headed Cowbirds Prefer Less Intense Male Displays

Sexual selection theory predicts that females should prefer males with the most intense courtship displays. However, wing-spread song displays that male brown-headed cowbirds (Molothrus ater) direct at females are generally less intense than versions of this display that are directed at other males. Because male-directed displays are used in aggressive signaling, we hypothesized that females should prefer lower intensity performances of this display. To test this hypothesis, we played audiovisual recordings showing the same males performing both high intensity male-directed and low intensity female-directed displays to females (N = 8) and recorded the females' copulation solicitation display (CSD) responses. All eight females responded strongly to both categories of playbacks but were more sexually stimulated by the low intensity female-directed displays. Because each pair of high and low intensity playback videos had the exact same audio track, the divergent responses of females must have been based on differences in the visual content of the displays shown in the videos. Preferences female cowbirds show in acoustic CSD studies are correlated with mate choice in field and captivity studies and this is also likely to be true for preferences elucidated by playback of audiovisual displays. Female preferences for low intensity female-directed displays may explain why male cowbirds rarely use high intensity displays when signaling to females. Repetitive high intensity displays may demonstrate a male's current condition and explain why these displays are used in male-male interactions which can escalate into physical fights in which males in poorer condition could be injured or killed. This is the first study in songbirds to use audiovisual playbacks to assess how female sexual behavior varies in response to variation in a male visual display

Electronic structures of Pd(II) dimers.

The Pd(II) dimers [(2-phenylpyridine)Pd(mu-X)](2) and [(2-p-tolylpyridine)Pd(mu-X)](2) (X = OAc or TFA) do not exhibit the expected planar geometry (of approximate D(2h) symmetry) but instead resemble an open "clamshell" in which the acetate ligands are perpendicular to the plane containing the Pd atoms and 2-arylpyridine ligands, with the Pd atoms brought quite close to one another (approximate distance 2.85 A). The molecules adopt this unusual geometry in part because of a d(8)-d(8) bonding interaction between the two Pd centers. The Pd-Pd dimers exhibit two successive one-electron oxidations: Pd(II)-Pd(II) to Pd(II)-Pd(III) to Pd(III)-Pd(III). Photophysical measurements reveal clear differences in the UV-visible and low-temperature fluorescence spectra between the clamshell dimers and related planar dimeric [(2-phenylpyridine)Pd(mu-Cl)](2) and monomeric [(2-phenylpyridine)Pd(en)][Cl] (en = ethylenediamine) complexes that do not have any close Pd-Pd contacts. Density functional theory and atoms in molecules analyses confirm the presence of a Pd-Pd bonding interaction in [(2-phenylpyridine)Pd(mu-X)](2) and show that the highest occupied molecular orbital is a d(z(2)) sigma* Pd-Pd antibonding orbital, while the lowest unoccupied molecular orbital and close-lying empty orbitals are mainly located on the 2-phenylpyridine rings. Computational analyses of other Pd(II)-Pd(II) dimers that have short Pd-Pd distances yield an orbital ordering similar to that of [(2-phenylpyridine)Pd(mu-X)](2), but quite different from that found for d(8)-d(8) dimers of Rh, Ir, and Pt. This difference in orbital ordering arises because of the unusually large energy gap between the 4d and 5p orbitals in Pd and may explain why Pd d(8)-d(8) dimers do not exhibit the distinctive photophysical properties of related Rh, Ir, and Pt species

Ambient methane functionalization initiated by electrochemical oxidation of a vanadium (V)-oxo dimer

The abundant yet widely distributed methane resources require efficient conversion of methane into liquid chemicals, whereas an ambient selective process with minimal infrastructure support remains to be demonstrated. Here we report selective electrochemical oxidation of CH4 to methyl bisulfate (CH3OSO3H) at ambient pressure and room temperature with a molecular catalyst of vanadium (V)-oxo dimer. This water-tolerant, earth-abundant catalyst possesses a low activation energy (10.8 kcal mol‒1) and a high turnover frequency (483 and 1336 hr-1 at 1-bar and 3-bar pure CH4, respectively). The catalytic system electrochemically converts natural gas mixture into liquid products under ambient conditions over 240 h with a Faradaic efficiency of 90% and turnover numbers exceeding 100,000. This tentatively proposed mechanism is applicable to other d0 early transition metal species and represents a new scalable approach that helps mitigate the flaring or direct emission of natural gas at remote locations

Catalytic C–H bond silylation of aromatic heterocycles

This protocol describes a method for the direct silylation of the carbon–hydrogen (C–H) bond of aromatic heterocycles using inexpensive and abundant potassium tert-butoxide (KOt-Bu) as the catalyst. This catalytic cross-dehydrogenative coupling of simple hydrosilanes and various electron-rich aromatic heterocycles enables the synthesis of valuable silylated heteroarenes. The products thus obtained can be used as versatile intermediates, which facilitate the divergent synthesis of pharmaceutically relevant compound libraries from a single Si-containing building block. Moreover, a variety of complex Si-containing motifs, such as those produced by this protocol, are being actively investigated as next-generation therapeutic agents, because they can have improved pharmacokinetic properties compared with the original all-carbon drug molecules. Current competing methods for C–H bond silylation tend to be incompatible with functionalities, such as Lewis-basic heterocycles, that are often found in pharmaceutical substances; this leaves de novo synthesis as the principal strategy for preparation of the target sila-drug analog. Moreover, competing methods tend to be limited in the scope of hydrosilane that can be used, which restricts the breadth of silicon-containing small molecules that can be accessed. The approach outlined in this protocol enables the chemoselective and regioselective late-stage silylation of small heterocycles, including drugs and drug derivatives, with a broad array of hydrosilanes in the absence of precious metal catalysts, stoichiometric reagents, sacrificial hydrogen acceptors or high temperatures. Moreover, H_2 is the only by-product generated. The procedure normally requires 48–75 h to be completed

Computational studies of the solid-state molecular organometallic (SMOM) chemistry of Rh σ-alkane complexes

A review of computational studies on the structures, bonding and reactivity of rhodium σ-alkane complexes in the solid state is presented. These complexes of the general form [(R2P(CH2)nPR2)Rh(alkane)][BArF 4] (where ArF = 3,5-(CF3)2C6H3) are formed via solid/gas hydrogenation of alkene precursors, often in single-crystal-to-single-crystal (SC-SC) transformations. Molecular and periodic density functional theory (DFT) calculations complement experimental characterisation techniques (X-ray, solid-state NMR) to provide a detailed picture of the structure and bonding in these species. These σ-alkane complexes exhibit reactivity in the solid state, undergoing fluxional processes, and access different alkane binding modes that link to C-H activation and H/D exchange. The mechanisms of several of these processes have been defined using periodic DFT calculations which provide excellent quantitative agreement with the available experimental activation barriers. A comparison of computed results derived from periodic DFT calculations, where the full solid-state environment is taken into account, with simple model calculations using the isolated molecular cations highlights the importance of modelling the solid state to reproduce the structures of these alkane complexes. The solid-state environment can also have a significant impact on the computed reaction energetics