A framework for constructing linear free energy relationships to design molecular transition metal catalysts

2021 ◽  
Author(s):  
Zhenzhuo Lan ◽  
Shaama Mallikarjun Sharada
Keyword(s):  
Free Energy ◽  
Transition Metal ◽  
Transition Metal Complexes ◽  
General Procedure ◽  
Transition Metal Catalysts ◽  
Linear Free Energy Relationships ◽  
Computational Framework ◽  
Linear Free Energy ◽  
Molecular Transition ◽  
Energy Relationships

A computational framework for ligand-driven design of transition metal complexes is presented in this work. We propose a general procedure for the construction of active site-specific linear free energy relationships...

Linear free energy relationships for transition metal chemistry: case study of CH activation with copper–oxygen complexes

2020 ◽  
Vol 22 (14) ◽  
pp. 7155-7159 ◽  
Author(s):  
Zhenzhuo Lan ◽  
Shaama Mallikarjun Sharada
Keyword(s):  
Free Energy ◽  
Transition Metal ◽  
Transition Metal Complexes ◽  
Linear Free Energy Relationships ◽  
Computational Framework ◽  
Ch Activation ◽  
Linear Free Energy ◽  
Energy Relationships ◽  
Oxygen Complexes

We propose a computational framework for developing Taft-like linear free energy relationships to characterize steric effects on the catalytic activity of transition metal complexes.

Linear Free Energy Relationships for Transition Metal Complex Chemistry: Opportunity or Pipe Dream?

2019 ◽  
Author(s):  
Zhenzhuo Lan ◽  
Shaama Mallikarjun Sharada
Keyword(s):  
Free Energy ◽  
Transition Metal ◽  
Catalyst Design ◽  
Energy Decomposition Analysis ◽  
Linear Free Energy Relationship ◽  
Linear Free Energy Relationships ◽  
Structural Descriptors ◽  
Linear Free Energy ◽  
Energy Relationships ◽  
Geometric Effects

We propose a computational framework for developing Taft-like linear free energy relationships to characterize steric effects on the catalytic activity of transition metal complexes. The framework uses the activation strain model and energy decomposition analysis to isolate electronic and geometric effects, and identifies structural descriptors to construct the linear relationship. We demonstrate proof-of-principle for CH activation with enzyme-inspired [Cu2O2]2+ complexes, each coordinated to two identical bidentate diamine N-donors. Electronic effects are largely similar across the chosen systems and geometric effects – quantified by strain energies – are accurately captured by a linear combination of two structural descriptors. A powerful linear free energy relationship emerges that is both transferable to asymmetrically substituted complexes and independent of choice of theory. We outline steps for expanding this approach to create a generalizable Taft framework for inorganic catalyst design.

Linear Free Energy Relationships for Transition Metal Complex Chemistry: Opportunity or Pipe Dream?

2019 ◽  
Author(s):  
Zhenzhuo Lan ◽  
Shaama Mallikarjun Sharada
Keyword(s):  
Free Energy ◽  
Transition Metal ◽  
Catalyst Design ◽  
Energy Decomposition Analysis ◽  
Linear Free Energy Relationship ◽  
Linear Free Energy Relationships ◽  
Structural Descriptors ◽  
Linear Free Energy ◽  
Energy Relationships ◽  
Geometric Effects

We propose a computational framework for developing Taft-like linear free energy relationships to characterize steric effects on the catalytic activity of transition metal complexes. The framework uses the activation strain model and energy decomposition analysis to isolate electronic and geometric effects, and identifies structural descriptors to construct the linear relationship. We demonstrate proof-of-principle for CH activation with enzyme-inspired [Cu2O2]2+ complexes, each coordinated to two identical bidentate diamine N-donors. Electronic effects are largely similar across the chosen systems and geometric effects – quantified by strain energies – are accurately captured by a linear combination of two structural descriptors. A powerful linear free energy relationship emerges that is both transferable to asymmetrically substituted complexes and independent of choice of theory. We outline steps for expanding this approach to create a generalizable Taft framework for inorganic catalyst design.

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