Altering Linear Scaling Relationships on Metal Catalysts via Ligand–Adsorbate Hydrogen Bonding

2021 ◽  
Author(s):  
Alexander H. Jenkins ◽  
Charles B. Musgrave ◽  
J. Will Medlin
Keyword(s):  
Hydrogen Bonding ◽  
Metal Catalysts ◽  
Linear Scaling ◽  
Scaling Relationships

Activity-Based Screening of Homogeneous Catalysts through the Rapid Assessment of Theoretically Derived Turnover Frequencies

2019 ◽  
Author(s):  
Matthew Wodrich ◽  
Boodsarin Sawatlon ◽  
Ephrath Solel ◽  
sebastian kozuch ◽  
Clemence Corminboeuf
Keyword(s):  
Free Energy ◽  
Rapid Assessment ◽  
Linear Scaling ◽  
Computational Studies ◽  
Turnover Frequency ◽  
Turnover Number ◽  
Pincer Ligand ◽  
Scaling Relationships ◽  
Energy Profiles ◽  
Hydrogenation Of Co

In homogeneous catalysis, the turnover frequency (TOF) and turnover number (TON) are the most commonly used quantities that experimentally describe catalytic activity. Computational studies, on the other hand, generally yield the ubiquitous free energy profile, which only provides the relative heights of different intermediates and transition states for a given reaction mechanism. This information, however, can be converted into a theoretical TOF through use of the energy span model. Clearly, directly computing turnover frequencies not only allows easy comparison of the activity of different catalysts, but also provides a means of directly comparing theory and experiment. Nonetheless, obtaining detailed free energy profiles for many catalysts is computationally costly. To overcome this and accelerate the rate at which prospective catalysts can be screened, here we use linear scaling relationships in tandem with the energy span model to create volcano plots that relate an easily and quickly computed energetic descriptor variable with a catalyst’s turnover frequency. As a demonstration of their ability, we use these “TOF volcanoes” to rapidly screen prospective transition metal/pincer-ligand catalysts based on activity in facilitating the hydrogenation of CO<sub>2</sub>to formate.

scholarly journals Linear scaling relationships and volcano plots in homogeneous catalysis – revisiting the Suzuki reaction

2015 ◽  
Vol 6 (12) ◽  
pp. 6754-6761 ◽  
Author(s):  
Michael Busch ◽  
Matthew D. Wodrich ◽  
Clémence Corminboeuf
Keyword(s):  
Homogeneous Catalysis ◽  
Heterogeneous Catalysts ◽  
Suzuki Reaction ◽  
Homogeneous System ◽  
Linear Scaling ◽  
Scaling Relationships ◽  
Volcano Plots ◽  
System P ◽  
First Time

Volcano plots, commonly used to identify attractive heterogeneous catalysts are applied, for the first time, to a prototypical homogeneous system.

Scaling relationships and volcano plots of homogeneous transition metal catalysis

2020 ◽  
Vol 49 (12) ◽  
pp. 3652-3657
Author(s):  
Li-Cheng Yang ◽  
Xin Hong
Keyword(s):  
Transition Metal ◽  
Transition Metal Catalysis ◽  
Linear Scaling ◽  
Metal Catalysis ◽  
Scaling Relationships ◽  
Volcano Plots

This Frontier article highlights the recent applications of linear scaling relationships and volcano plots in homogeneous transition metal catalysis.

scholarly journals Strategies to break linear scaling relationships

2019 ◽  
Vol 2 (11) ◽  
pp. 971-976 ◽  
Author(s):  
Javier Pérez-Ramírez ◽  
Núria López
Keyword(s):  
Linear Scaling ◽  
Scaling Relationships

Activity-Based Screening of Homogeneous Catalysts through the Rapid Assessment of Theoretically Derived Turnover Frequencies

2019 ◽  
Author(s):  
Matthew Wodrich ◽  
Boodsarin Sawatlon ◽  
Ephrath Solel ◽  
sebastian kozuch ◽  
Clemence Corminboeuf
Keyword(s):  
Free Energy ◽  
Rapid Assessment ◽  
Linear Scaling ◽  
Computational Studies ◽  
Turnover Frequency ◽  
Turnover Number ◽  
Pincer Ligand ◽  
Scaling Relationships ◽  
Energy Profiles ◽  
Hydrogenation Of Co

In homogeneous catalysis, the turnover frequency (TOF) and turnover number (TON) are the most commonly used quantities that experimentally describe catalytic activity. Computational studies, on the other hand, generally yield the ubiquitous free energy profile, which only provides the relative heights of different intermediates and transition states for a given reaction mechanism. This information, however, can be converted into a theoretical TOF through use of the energy span model. Clearly, directly computing turnover frequencies not only allows easy comparison of the activity of different catalysts, but also provides a means of directly comparing theory and experiment. Nonetheless, obtaining detailed free energy profiles for many catalysts is computationally costly. To overcome this and accelerate the rate at which prospective catalysts can be screened, here we use linear scaling relationships in tandem with the energy span model to create volcano plots that relate an easily and quickly computed energetic descriptor variable with a catalyst’s turnover frequency. As a demonstration of their ability, we use these “TOF volcanoes” to rapidly screen prospective transition metal/pincer-ligand catalysts based on activity in facilitating the hydrogenation of CO<sub>2</sub>to formate.

scholarly journals Beyond hydrogen bonding: recent trends of outer sphere interactions in transition metal catalysis

2021 ◽  
Author(s):  
Jonathan Trouvé ◽  
Rafael Gramage-Doria
Keyword(s):  
Hydrogen Bonding ◽  
Transition Metal ◽  
Coordination Sphere ◽  
Outer Sphere ◽  
Metal Catalysts ◽  
Transition Metal Catalysts ◽  
Transition Metal Catalysis ◽  
Great Promise ◽  
Metal Catalysis ◽  
Recent Trends

The implementation of interactions beyond hydrogen bonding in the 2nd coordination sphere of transition metal catalysts is rare. However, it has already shown great promise in last 5 years, providing new tools to control the activity and selectivity as here reviewed.

Phylogenetic variation in hind-limb bone scaling of flightless theropods

Paleobiology ◽  
2016 ◽  
Vol 43 (1) ◽  
pp. 129-143 ◽  
Author(s):  
Nicholas R. Chan
Keyword(s):  
Weight Bearing ◽  
Center Of Mass ◽  
Linear Scaling ◽  
Large Species ◽  
Limb Bone ◽  
Limb Bones ◽  
Scaling Relationships ◽  
Taxonomic Groups ◽  
Leg Bones ◽  
Polynomial Regressions

AbstractThe robusticity of the weight-bearing limbs of large terrestrial animals is expected to increase at a more rapid rate than in their smaller relatives. This scaling has been hypothesized to allow large species to maintain stresses in the limb bones that are similar to those seen in smaller ones. Curvilinear scaling has previously been found in mammals and nonavian theropods but has not been demonstrated in birds. In this study, polynomial regressions of leg-bone length and circumference in terrestrial flightless birds were carried out to test for a relationship similar to that seen in nonavian theropods. Flightless birds exhibit curvilinear scaling, with the femora of large taxa becoming thicker relative to length at a greater rate than in smaller taxa. Evidence was found for nonlinear scaling in the leg bones of nonavian theropods. However, unlike in avians, there is also phylogenetic variation between taxonomic groups, with tyrannosaur leg bones in particular scaling differently than other groups. Phylogenetically corrected quadratic regressions and separate analyses of taxonomic groupings found little phylogenetic variation in flightless birds. It is suggested here that the nonlinear scaling seen in avian femora is due to the need to maintain the position of the knee under a more anterior center of mass, thereby restricting femoral length. The femur of nonavian theropods is not so constrained, with greater variability of the linear scaling relationships between clades. Phylogenetic variation in limb-bone scaling may broaden the errors for mass-predictive scaling equations based on limb-bone measurements of nonavian theropods.

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