A contact binary satellite of the asteroid (152830) Dinkinesh.

Asteroids with diameters less than about 5 km have complex histories because they are small enough for radiative torques (that is, YORP, short for the Yarkovsky-O'Keefe-Radzievskii-Paddack effect) to be a notable factor in their evolution. (152830) Dinkinesh is a small asteroid orbiting the Sun near the inner edge of the main asteroid belt with a heliocentric semimajor axis of 2.19 AU; its S-type spectrum is typical of bodies in this part of the main belt.

Strained-layer-superlattice-based compact thermal imager for the International Space Station.

The compact thermal imager (CTI) is a dual-band, strained-layer-superlattice (SLS) detector-based instrument that was installed on the exterior of the International Space Station (ISS) in conjunction with the third Robotic Refueling Mission 3 (RRM3) in 2018. The CTI serves as a pathfinder for future thermal infrared capability on Landsat. The CTI incorporates an SLS hybrid, a dual-band 3-5 and 8-10 μm, electrically switchable, 320×256 array with 30   pixels, bonded to an Indigo ISC0903 Readout Integrated Circuit (ROIC).

Comparisons of MNSvs. bipyridine as redox-active ligands to manganese and rhenium in (L-L)M'(CO)Cl complexes.

The bipyridine ligand is renowned as a photo- and redox-active ligand in catalysis; the latter has been particularly explored in the complex Re(bipy)(CO)Cl for CO reduction. We ask whether a bidentate, redox-active MNS metallodithiolate ligand in heterobimetallic complexes of Mn and Re might similarly serve as a receptor and conduit of electrons. In order to assess the electrochemical features of such designed bimetallics, a series of complexes featuring redox active MNS metallodithiolates, with M = Ni, {Fe(NO)}, and {Co(NO)}, bound to M'(CO)X, where M' = Mn and Re, were synthesized and characterized using IR and EPR spectroscopies, X-ray diffraction, cyclic voltammetry, and density functional theory (DFT) computations.

Hemilabile Bridging Thiolates as Proton Shuttles in Bioinspired H Production Electrocatalysts.

Synthetic analogues and computationally assisted structure-function analyses have been used to explore the features that control proton-electron and proton-hydride coupling in electrocatalysts inspired by the [NiFe]-hydrogenase active site. Of the bimetallic complexes derived from aggregation of the dithiolato complexes MNS (NS = bismercaptoethane diazacycloheptane; M = Ni or Fe(NO)) with (η-CH)Fe(CO) (the Fe' component) or (η-CH)Fe(CO), Fe″, which yielded Ni-Fe', Fe-Fe', Ni-Fe″, and Fe-Fe″, respectively, both Ni-Fe' and Fe-Fe' were determined to be active electrocatalysts for H production in the presence of trifluoroacetic acid. Correlations of electrochemical potentials and H generation are consistent with calculated parameters in a predicted mechanism that delineates the order of addition of electrons and protons, the role of the redox-active, noninnocent NO ligand in electron uptake, the necessity for Fe'-S bond breaking (or the hemilability of the metallodithiolate ligand), and hydride-proton coupling routes.

Ligand Displacement Reaction Paths in a Diiron Hydrogenase Active Site Model Complex.

The mechanism and energetics of CO, 1-hexene, and 1-hexyne substitution from the complexes (SBenz)2 [Fe2 (CO)6 ] (SBenz=SCH2 Ph) (1-CO), (SBenz)2 [Fe2 (CO)5 (η(2) -1-hexene)] (1-(η(2) -1-hexene)), and (SBenz)2 [Fe2 (CO)5 (η(2) -1-hexyne)] (1-(η(2) -1-hexyne)) were studied by using time-resolved infrared spectroscopy. Exchange of both CO and 1-hexyne by P(OEt)3 and pyridine, respectively, proceeds by a bimolecular mechanism. As similar activation enthalpies are obtained for both reactions, the rate-determining step in both cases is assumed to be the rotation of the Fe(CO)2 L (L=CO or 1-hexyne) unit to accommodate the incoming ligand.

Cyanide-bridged iron complexes as biomimetics of tri-iron arrangements in maturases of the H cluster of the di-iron hydrogenase.

Developing from certain catalytic processes required for ancient life forms, the H processing enzymes [NiFe]- and [FeFe]-hydrogenase (Hase) have active sites that are organometallic in composition, possessing carbon monoxide and cyanide as ligands. Simple synthetic analogues of the 2Fe portion of the active site of [FeFe]-Hase have been shown to dock into the empty carrier (maturation) protein, apo-Hyd-F, the bridging ability of a terminal cyanide ligand from a low valent FeFe unit to the iron of a 4Fe4S cluster of Hyd-F, with spectral evidence indicating CN isomerization during the coupling process (Berggren, , , 2013, , 66-70). To probe the requirements for such cyanide couplings, we have prepared and characterized four cyanide-bridged analogues of 3-Fe systems with features related to the organoiron moiety within the loaded HydF protein.

Catalysis and Mechanism of H2 Release from Amine-Boranes by Diiron Complexes.

Studies focused on the dehydrogenation of amine-borane by diiron complexes that serve as well-characterized rudimentary models of the diiron subsite in [FeFe]-hydrogenase are reported. Complexes of formulation (μ-SCH2XCH2S)[Fe(CO)3]2, with X = CH2, CMe2, CEt2, NMe, NtBu, and NPh, 1-CO through 6-CO, respectively, were determined to be photocatalysts for release of H2 gas from a solution of H3B ← NHMe2 (B:A(s)), dissolved in THF. The thermal displacement of the tertiary amine-borane, H3B ← NEt3 (B:A(t)) from photochemically generated (μ-SCH2XCH2S)[Fe(CO)3][Fe(CO)2(μ-H)(BH2-NEt3)], 1-B:A(t) through 6-B:A(t), by P(OEt)3 was monitored by time-resolved FTIR spectroscopy.

Metallodithiolates as ligands to dinitrosyl iron complexes: toward the understanding of structures, equilibria, and spin coupling.

Metallodithiolate ligands are used to design heterobimetallic complexes by adduct formation through S-based reactivity. Such adducts of dinitrosyl iron were synthesized with two metalloligands, namely, Ni(bme-daco) and V≡O(bme-daco) (bme-daco = bismercaptoethane diazacyclooctane), and, for comparison, an N-heterocyclic carbene, namely, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (Imes), by cleavage of the (μ-I)2[Fe(NO)2]2 dimer of electronic configuration {Fe(NO)2}(9) (Enemark-Feltham notation). With Fe(NO)2I as Lewis acid acceptor, 1:1 adducts resulted for both the IMes·Fe(NO)2I, complex 2, and V≡O(bme-daco)·Fe(NO)2I, complex 4.

Versatile N2S2 nickel-dithiolates as mono- and bridging bidentate, S-donor ligands to gold(I).

Development of square planar cis-dithiolate nickel complexes as metallo S-donor ligands focuses on the synthesis and structures of gold(I) heterometallic clusters derived from assemblage with three NiN2S2 complexes: Ni(bme-daco), Ni(bme-dach) and Ni(ema)(2-) (bme-daco = (bismercaptoethanediazacyclooctane); bme-dach = bismercaptoethanediazacycloheptane; and ema = N,N'-ethylenebis-2-mercaptoacetamide). With Ph3PAuCl as the gold source, examples of simple S-aurolation retaining the PPh3 on Au(+) were obtained for [{Ni(bme-daco)}AuPPh3](+)Cl(-) and [{Ni(ema)}2Au4(PPh3)4], where the latter complex demonstrated unsupported aurophilic interactions between [{Ni(ema)}Au2(PPh3)2] units in its X-ray crystal structure (Au-Au = 3.054 and 3.

12C/13C ratio in ethane on titan and implications for methane's replenishment.

The (12)C/(13)C abundance ratio in ethane in the atmosphere of Titan has been measured at 822 cm(-1) from high spectral resolution ground-based observations. The value, 89(8), coincides with the telluric standard and also agrees with the ratio seen in the outer planets. It is almost identical to the result for ethane on Titan found by the composite infrared spectrometer (CIRS) on Cassini.

Polar lightning and decadal-scale cloud variability on Jupiter.

Although lightning has been seen on other planets, including Jupiter, polar lightning has been known only on Earth. Optical observations from the New Horizons spacecraft have identified lightning at high latitudes above Jupiter up to 80 degrees N and 74 degrees S. Lightning rates and optical powers were similar at each pole, and the mean optical flux is comparable to that at nonpolar latitudes, which is consistent with the notion that internal heat is the main driver of convection.