The rate constant for Cl + NH 3 f HCl + NH 2 has been measured over 290-570 K by the time-resolved resonance fluorescence technique. Ground-state Cl atoms were generated by 193 nm excimer laser photolysis of CCl 4 and reacted under pseudo-first-order conditions with excess NH 3 . The forward rate constant was fit by the expression k 1 ) (1.08 ( 0.05) × 10 -11 exp(-11.47 ( 0.16 kJ mol, where the uncertainties in the Arrhenius parameters are (1 σ and the 95% confidence limits for k 1 are (11%. To rationalize the activation energy, which is 7.4 kJ mol -1 below the endothermicity in the middle of the 1/T range, the potential energy surface was characterized with MPWB1K/6-31++G(2df,2p) theory. The products NH 2 + HCl form a hydrogen-bonded adduct, separated from Cl + NH 3 by a transition state lower in energy than the products. The rate constant for the reverse process k -1 was derived via modified transition state theory, and the computed k -1 exhibits a negative activation energy, which in combination with the experimental equilibrium constant yields k 1 in fair accord with experiment.
A dizinc phosphohydrolase enzyme model complex employing the dinucleating ligand 2,6-bis-[(bis-pyridin-2-ylmethyl-amino)methyl]-4-methylphenol (L1) was tested for binding to a series of 11 commercially available complexometric indicators in aqueous N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid (HEPES) buffer at pH 7.4, with the aim of determining the applicability of these indicators in indicator displacement assays (IDAs) under physiological conditions. Dissociation constants (Kd) were determined for 11 indicator-Zn2L1 complexes, spanning 2 orders of magnitude from 2.8 x 10(-4) M (alizarin red S) to 2.7 x 10(-6) M (bromo pyrogallol red). Phosphate and pyrophosphate were tested for their ability to displace bound indicator and produce a detectable colorimetric response. Three indicators (bromo pyrogallol red, mordant blue 9, and zincon) complex to Zn2L1 to form an indicator displacement assay selective for pyrophosphate over phosphate. Because selection of an indicator/analyte pair having appropriate relative Kd values is critical for their successful application in IDAs, the binding data for these 11 indicators should assist their extension to IDAs for other analytes.
The terphspan scaffold was employed to support a bis(N-heterocyclic carbene) ligand () that provides a m-terphenyl canopy over one side of its metal complexes. Single-crystal X-ray diffraction studies on a silver complex of {[Ag()]AgBr(2)}(2) revealed an unusual tetranuclear silver core with a Ag-Ag bond distance of 3.0241(8) A with as a trans-chelating ligand (C-Ag-C = 171 degrees ). A preliminary X-ray structure of pseudo-square planar [PdCl(2)()] showed a similar binding mode of (C-Pd-C = 177 degrees ). High yields were obtained in Suzuki-Miyaura coupling reactions utilizing [PdCl(2)()] as the procatalyst and the results were compared with analogous complexes of trans-spanning diphosphine () and diphosphinite () complexes. The diphosphinite complex, [PdCl(2)()], decomposes to [mu-ClPd(PPh(2)OH)(PPh(2)O)](2) at room temperature.
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