More Like this

1. Mechanochemical synthesis and structural analysis of trivalent lanthanide and uranium diphenylphosphinodiboranates

   https://doi.org/10.1039/d1dt01932e  

   Fetrow, Taylor V. ; Daly, Scott R. ( August 2021 , Dalton Transactions)

   Phosphinodiboranates (H 3 BPR 2 BH 3 − ) are a class of borohydrides that have merited a reputation as weakly coordinating anions, which is attributed in part to the dearth of coordination complexes known with transition metals, lanthanides, and actinides. We recently reported how K(H 3 BP t Bu 2 BH 3 ) exhibits sluggish salt elimination reactivity with f-metal halides in organic solvents such as Et 2 O and THF. Here we report how this reactivity appears to be further attenuated in solution when the t Bu groups attached to phosphorus are exchanged for R = Ph ormore »H, and we describe how mechanochemistry was used to overcome limited solution reactivity with K(H 3 BPPh 2 BH 3 ). Grinding three equivalents of K(H 3 BPPh 2 BH 3 ) with UI 3 (THF) 4 or LnI 3 (Ln = Ce, Pr, Nd) allowed homoleptic complexes with the empirical formulas U(H 3 BPPh 2 BH 3 ) 3 (1), Ce(H 3 BPPh 2 BH 3 ) 3 (2), Pr(H 3 BPPh 2 BH 3 ) 3 (3), and Nd(H 3 BPPh 2 BH 3 ) 3 (4) to be prepared and subsequently crystallized in good yields (50–80%). Single-crystal XRD studies revealed that all four complexes exist as dimers or coordination polymers in the solid-state, whereas 1 H and 11 B NMR spectra showed that they exist as a mixture of monomers and dimers in solution. Treating 4 with THF breaks up the dimer to yield the monomeric complex Nd(H 3 BPPh 2 BH 3 ) 3 (THF) 3 (4-THF). XRD studies revealed that 4-THF has one chelating and two dangling H 3 BPPh 2 BH 3 − ligands bound to the metal to accommodate binding of THF. In contrast to the results with K(H 3 BPPh 2 BH 3 ), attempting the same mechanochemical reactions with Na(H 3 BPH 2 BH 3 ) containing the simplest phosphinodiboranate were unsuccessful; only the partial metathesis product U(H 3 BPH 2 BH 3 )I 2 (THF) 3 (5) was isolated in poor yields. Despite these limitations, our results offer new examples showing how mechanochemistry can be used to rapidly synthesize molecular coordination complexes that are otherwise difficult to prepare using more traditional solution methods.« less
2. Freshwater Salinization Syndrome Alters Retention and Release of ‘Chemical Cocktails’ along Flowpaths:  from Stormwater Management to Urban Streams

   https://doi.org/10.1086/721469  

   Kaushal, Sujay ; Reimer, Jenna E. ; Mayer, Paul M. ; Shatkay, Ruth R. ; Maas, Carly ; Nguyen, William D. ; Boger, Walter L. ; Yaculak, Alexis M. ; Doody, Thomas R. ; Pennino, Michael ; et al ( June 2022 , Freshwater Science)

   Freshwater salinization syndrome (FSS) refers to the suite of interactive effects of salt ions on degradation of physical, biological,and social systems. Best management practices (BMPs), which are methods to effectively reduce runoff and nonpoint source pollution (stormwater, nutrients, sediments), do not typically consider management of salt pollution. We investigate impacts of FSS on mobilization of salts, nutrients, and metals in urban streams and storm water BMPs by analyzing original data on concentrations and fluxes of salts, nutrients, and metals from 7 urban watersheds in the Mid-Atlantic USA and synthesizing literature data. We also explore future critical research needs through amore »survey of practitioners and scientists. Our original data show 1) sharp pulses in concentrations of salt ions and metals in urban streams directly following both road salt events and stream restoration construction (e.g.,similar to the way concentrations increase during other soil disturbance activities); 2) sharp declines in pH (acidification) in response to road salt applications because of mobilization of H+ from soil exchange sites by Na+; 3) sharp increases inorganic matter from microbial and algal sources (based on fluorescence spectroscopy) in response to road salt applications, likely because of lysing cells and changes insolubility; 4) substantial retention (~30–40%) of Na+ in stormwater BMP sediments and floodplains in response to salinization; 5) increased ion exchange and mobilization of diverse salt ions (Na+, Ca2+, K+, Mg2+), nutrients(N, P), and trace metals(Cu, Sr) from stormwater BMPs and restored streams in response to FSS; 6) downstream increasing loads ofCl–, SO42–, Br–, F–,andI–along flowpaths through urbanstreams and P release from urban stormwater BMPs in response to salinization; and 7)a substantial annual reduction (>50%) in Na+concentrations in an urban stream when road salt applications were dramatically reduced, which suggests potential for ecosystem recovery. We compare our original results with published metrics of contaminant retention and release across a broad range of stormwater BMPs from North America and Europe.Overall, urban streams and stormwater BMPs consistently retain Na+ and Cl–but mobilize multiple contaminants based on salt types and salinity levels. Finally, we present our top 10 research questions regarding FSS impacts on urban streams and stormwater BMPs. Reducing diverse chemical cocktails of contaminants mobilized by freshwater salinization is a priority for effectively and holistically restoring urban waters.« less
3. Accelerating ethylene polymerization using secondary metal ions in tetrahydrofuran

   https://doi.org/10.1039/C9DT04288A  

   Xiao, Dawei ; Cai, Zhongzheng ; Do, Loi H. ( December 2019 , Dalton Transactions)

   We have prepared a new series of nickel phosphine phosphonate ester complexes that feature two metal-chelating polyethylene glycol (PEG) side arms. Metal binding and reactivity studies in polar solvents showed that they readily coordinate external cations, including alkali (Li + , Na + , K + ), alkaline (Mg 2+ , Ca 2+ ), transition (Sc 3+ , Co 2+ , Zn 2+ ), post-transition (Ga 3+ ), and lanthanide (La 3+ ) metals. Although olefin polymerization reactions are typically performed in non-polar solvents, which cannot solubilize +2 and +3 metal cations, we discovered that our nickel catalysts could promotemore »ethylene polymerization in neat tetrahydrofuran. This advance allowed us, for the first time, to systematically investigate the effects of a wide range of M + , M 2+ , and M 3+ ions on the reactivity of nickel olefin polymerization catalysts. In ethylene homopolymerization, the addition of Co(OTf) 2 to our nickel-PEG complexes provided the largest boost in activity (up to 11-fold, 2.7 × 10 6 g mol −1 h −1 ) compared to that in the absence of external salts. The catalyst enhancing effects of secondary metals were also observed in studies of ethylene and polar olefin ( e.g. , propyl vinyl ether, allyl butyl ether, methyl-10-undecenoate, and 5-acetoxy-1-pentene) copolymerization. Notably, combining either Co 2+ or Zn 2+ with our nickel complexes increased the rates of polymerization in the presence of propyl vinyl ether by about 5.0- and 2.4-fold, respectively. Although further studies are needed to elucidate the structural and mechanistic roles of the secondary metals, this work is an important advance toward the development of cation-switchable polymerization catalysts.« less
4. Binding energies of hydrated cobalt( ii ) by collision-induced dissociation and theoretical studies: evidence for a new critical size

   https://doi.org/10.1039/C7CP05828D  

   Coates, Rebecca A. ; Armentrout, P. B. ( January 2018 , Physical Chemistry Chemical Physics)

   The experimental sequential bond energies for loss of water from Co 2+ (H 2 O) x complexes, x = 5–11, are determined by threshold collision-induced dissociation (TCID) using a guided ion beam tandem mass spectrometer with a thermal electrospray ionization source. Kinetic energy dependent TCID cross sections are analyzed to yield 0 K thresholds for sequential loss of neutral water molecules. The thresholds are converted from 0 to 298 K values to give hydration enthalpies and free energies. Theoretical geometry optimizations and single point energy calculations at several levels of theory are performed for the reactant and product ion complexes.more »Theoretical bond energies for ground structures are used for direct comparison with experimental values to obtain structural information on these complexes. In addition, the dissociative charge separation process, Co 2+ (H 2 O) x → CoOH + (H 2 O) m + H + (H 2 O) x−m−1 , is observed at x = 4, 6, and 7 in competition with primary water loss products. Energies for the charge separation rate-limiting transition states are calculated and compared to experimental threshold measurements. Results suggest that the critical size for which charge separation is energetically favored over water loss is x crit = 6, in contrast to lower values in previous literature reports.« less
5. Close-up view of a luminous star-forming galaxy at z = 2.95

   https://doi.org/10.1051/0004-6361/202039743  

   Berta, S. ; Young, A. J. ; Cox, P. ; Neri, R. ; Jones, B. M. ; Baker, A. J. ; Omont, A. ; Dunne, L. ; Carnero Rosell, A. ; Marchetti, L. ; et al ( February 2021 , Astronomy & Astrophysics)

   Exploiting the sensitivity of the IRAM NOrthern Extended Millimeter Array (NOEMA) and its ability to process large instantaneous bandwidths, we have studied the morphology and other properties of the molecular gas and dust in the star forming galaxy, H-ATLAS J131611.5+281219 (HerBS-89a), at z = 2.95. High angular resolution (0 . ″3) images reveal a partial 1 . ″0 diameter Einstein ring in the dust continuum emission and the molecular emission lines of 12 CO(9−8) and H 2 O(2 02  − 1 11 ). Together with lower angular resolution (0 . ″6) images, we report the detection of a series of molecularmore »lines including the three fundamental transitions of the molecular ion OH + , namely (1 1  − 0 1 ), (1 2  − 0 1 ), and (1 0  − 0 1 ), seen in absorption; the molecular ion CH + (1 − 0) seen in absorption, and tentatively in emission; two transitions of amidogen (NH 2 ), namely (2 02  − 1 11 ) and (2 20  − 2 11 ) seen in emission; and HCN(11 − 10) and/or NH(1 2  − 0 1 ) seen in absorption. The NOEMA data are complemented with Very Large Array data tracing the 12 CO(1 − 0) emission line, which provides a measurement of the total mass of molecular gas and an anchor for a CO excitation analysis. In addition, we present Hubble Space Telescope imaging that reveals the foreground lensing galaxy in the near-infrared (1.15  μ m). Together with photometric data from the Gran Telescopio Canarias, we derive a photometric redshift of z phot = 0.9 −0.5 +0.3 for the foreground lensing galaxy. Modeling the lensing of HerBS-89a, we reconstruct the dust continuum (magnified by a factor μ  ≃ 5.0) and molecular emission lines (magnified by μ  ∼ 4 − 5) in the source plane, which probe scales of ∼0 . ″1 (or 800 pc). The 12 CO(9 − 8) and H 2 O(2 02  − 1 11 ) emission lines have comparable spatial and kinematic distributions; the source-plane reconstructions do not clearly distinguish between a one-component and a two-component scenario, but the latter, which reveals two compact rotating components with sizes of ≈1 kpc that are likely merging, more naturally accounts for the broad line widths observed in HerBS-89a. In the core of HerBS-89a, very dense gas with n H 2  ∼ 10 7 − 9 cm −3 is revealed by the NH 2 emission lines and the possible HCN(11 − 10) absorption line. HerBS-89a is a powerful star forming galaxy with a molecular gas mass of M mol  = (2.1 ± 0.4) × 10 11   M ⊙ , an infrared luminosity of L IR  = (4.6 ± 0.4) × 10 12   L ⊙ , and a dust mass of M dust  = (2.6 ± 0.2) × 10 9   M ⊙ , yielding a dust-to-gas ratio δ GDR  ≈ 80. We derive a star formation rate SFR = 614 ± 59  M ⊙ yr −1 and a depletion timescale τ depl  = (3.4 ± 1.0) × 10 8 years. The OH + and CH + absorption lines, which trace low (∼100 cm −3 ) density molecular gas, all have their main velocity component red-shifted by Δ V  ∼ 100 km s −1 relative to the global CO reservoir. We argue that these absorption lines trace a rare example of gas inflow toward the center of a galaxy, indicating that HerBS-89a is accreting gas from its surroundings.« less