Si–H Activation in an Iridium Nitrido ComplexA Mechanistic and Theoretical Study

Si–H activation in triethyl- and triarylsilanes by a square-planar pyridine-diimine iridium complex with a terminal nitrido unit leads to the corresponding silyl amido complexes, which were unambiguously characterized by X-ray crystallography. Based on detailed combined kinetic and theoretical studies (DFT), direct addition of the Si–H bond to the iridium nitrido unit is proposed. The electronic propensities of the transition states for the Si–H activation were probed with a Hammett series of <i>para</i>-substituted triarylsilanes HSi­(C₆H₅)₂(4-C₆H₄-X). Based on the combination of experimental and theoretical studies, two independent pathways for this process are proposed, which point toward an ambiphilic propensity of the nitrido unit. Alternative pathways and the charge transfer in the transition states were also investigated. Furthermore, the barriers for the related H–H and C–H activation processes in dihydrogen and methane were analyzed

Si–H Activation in an Iridium Nitrido ComplexA Mechanistic and Theoretical Study

Si–H activation in triethyl- and triarylsilanes by a square-planar pyridine-diimine iridium complex with a terminal nitrido unit leads to the corresponding silyl amido complexes, which were unambiguously characterized by X-ray crystallography. Based on detailed combined kinetic and theoretical studies (DFT), direct addition of the Si–H bond to the iridium nitrido unit is proposed. The electronic propensities of the transition states for the Si–H activation were probed with a Hammett series of <i>para</i>-substituted triarylsilanes HSi­(C₆H₅)₂(4-C₆H₄-X). Based on the combination of experimental and theoretical studies, two independent pathways for this process are proposed, which point toward an ambiphilic propensity of the nitrido unit. Alternative pathways and the charge transfer in the transition states were also investigated. Furthermore, the barriers for the related H–H and C–H activation processes in dihydrogen and methane were analyzed

Si–H Activation in an Iridium Nitrido ComplexA Mechanistic and Theoretical Study

Si–H activation in triethyl- and triarylsilanes by a square-planar pyridine-diimine iridium complex with a terminal nitrido unit leads to the corresponding silyl amido complexes, which were unambiguously characterized by X-ray crystallography. Based on detailed combined kinetic and theoretical studies (DFT), direct addition of the Si–H bond to the iridium nitrido unit is proposed. The electronic propensities of the transition states for the Si–H activation were probed with a Hammett series of <i>para</i>-substituted triarylsilanes HSi­(C₆H₅)₂(4-C₆H₄-X). Based on the combination of experimental and theoretical studies, two independent pathways for this process are proposed, which point toward an ambiphilic propensity of the nitrido unit. Alternative pathways and the charge transfer in the transition states were also investigated. Furthermore, the barriers for the related H–H and C–H activation processes in dihydrogen and methane were analyzed

Si–H Activation in an Iridium Nitrido ComplexA Mechanistic and Theoretical Study

Si–H activation in triethyl- and triarylsilanes by a square-planar pyridine-diimine iridium complex with a terminal nitrido unit leads to the corresponding silyl amido complexes, which were unambiguously characterized by X-ray crystallography. Based on detailed combined kinetic and theoretical studies (DFT), direct addition of the Si–H bond to the iridium nitrido unit is proposed. The electronic propensities of the transition states for the Si–H activation were probed with a Hammett series of <i>para</i>-substituted triarylsilanes HSi­(C₆H₅)₂(4-C₆H₄-X). Based on the combination of experimental and theoretical studies, two independent pathways for this process are proposed, which point toward an ambiphilic propensity of the nitrido unit. Alternative pathways and the charge transfer in the transition states were also investigated. Furthermore, the barriers for the related H–H and C–H activation processes in dihydrogen and methane were analyzed

Si–H Activation in an Iridium Nitrido ComplexA Mechanistic and Theoretical Study

Si–H activation in triethyl- and triarylsilanes by a square-planar pyridine-diimine iridium complex with a terminal nitrido unit leads to the corresponding silyl amido complexes, which were unambiguously characterized by X-ray crystallography. Based on detailed combined kinetic and theoretical studies (DFT), direct addition of the Si–H bond to the iridium nitrido unit is proposed. The electronic propensities of the transition states for the Si–H activation were probed with a Hammett series of <i>para</i>-substituted triarylsilanes HSi­(C₆H₅)₂(4-C₆H₄-X). Based on the combination of experimental and theoretical studies, two independent pathways for this process are proposed, which point toward an ambiphilic propensity of the nitrido unit. Alternative pathways and the charge transfer in the transition states were also investigated. Furthermore, the barriers for the related H–H and C–H activation processes in dihydrogen and methane were analyzed

The flowchart of MINErosion 2 and 3.4 models.

<p>The flowchart of MINErosion 2 and 3.4 models.</p

The selected storm events for spoil’s covered plots used to validate MINErosion 3.1.

<p>[<a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0194230#pone.0194230.ref025" target="_blank">25</a>]. Treatments were SpBa: Bare plots covered with spoil; SpTr: Plots covered with spoil and with trees as a vegetation cover; SpPa: Plots covered with spoil and with pastures as a vegetation cover, S %: Slope %.</p

Effect of consolidation on decreasing soil erodibility (K_MUSLE).

<p>Consolidation were a result of repeated wetting and drying and the presence of roots but not the above ground vegetation. (adapted from [<a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0194230#pone.0194230.ref017" target="_blank">17</a>, <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0194230#pone.0194230.ref018" target="_blank">18</a>]).</p

The selected storm events for soil’s covered plots used to validate MINErosion 3.1.

<p>[<a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0194230#pone.0194230.ref025" target="_blank">25</a>] Treatments were SoBa: Bare plots covered with soil; SoTr: Plots covered with soil and with trees as a vegetation cover; SoPa: Plots covered with soil and with pastures as a vegetation cover, S %: slope %.</p

Relative soil loss as affected by vegetation type (tussocky Rhodes vs stoloniferous Sabi grasses) [13].

<p>Relative soil loss as affected by vegetation type (tussocky Rhodes vs stoloniferous Sabi grasses) [<a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0194230#pone.0194230.ref013" target="_blank">13</a>].</p