Computational Assessment and Understanding of C6 Product Selectivity for Chromium Phosphinoamidine Catalyzed Ethylene Trimerization

Author(s):  
Nathan Morgan ◽  
Steven M. Maley ◽  
Doo-Hyun Kwon ◽  
Michael S. Webster-Gardiner ◽  
Brooke L. Small ◽  
...  
2021 ◽  
Author(s):  
Daniel Ess ◽  
Nathan Morgan ◽  
Steven Maley ◽  
Doo-Hyun Kwon ◽  
Michael Webster-Gardiner ◽  
...  

One approach to selectively generate 1-hexene is through ethylene trimerization using highly active Cr N-phosphinoamidine catalysts ((P,N)Cr). Depending on the ligand, (P,N)Cr catalysts can either generate nearly pure 1-hexene or form 1-hexene with significant mixtures of other C6 mass products, for example methylenecyclopentane. Here we report DFT transition state modeling examining 1-hexene catalysis pathways as well as pathways that lead to alternative C6 mass products. This provided qualitative and semi-quantitative modeling of the experimental 1-hexene purity values for several (P,N)Cr catalysts. Consistent with previous computational studies, the key 1-hexene purity-determining transition states were determined to be β-hydrogen transfer structures from the metallacycloheptane intermediate. The origin of selectivity for these (P,N)Cr catalysts can be attributed to steric effects in the transition-state structure with coordinated ethylene that leads to C6 impurities.


Author(s):  
Max Roemer ◽  
Vinicius Romero Gonçales ◽  
Sinead Teresa Keaveney ◽  
Indrek Pernik ◽  
Jiaxin Lian ◽  
...  

A series of Rh- and Ir-hybrid catalysts with varying tether lengths has been prepared by immobilization of RhI, RhIII and IrIII complexes on carbon black via radical grafting. The performance...


2021 ◽  
Author(s):  
Derik Wilbers ◽  
Joseph Brehm ◽  
Richard Lewis ◽  
Jacqueline Van Marwijk ◽  
Thomas Davies ◽  
...  

The combination of heterogeneous catalysis and biocatalysis into one-pot reaction cascades is a potential approach to integrate enzymatic transformations into existing chemical infrastructure. Peroxygenases, which can achieve clean C-H activation,...


Author(s):  
Apurv Saxena ◽  
Wipula Liyanage ◽  
Jahangir Masud ◽  
Shubhender Kapila ◽  
Manashi Nath

Simple, binary Cu2Se has been reported for electrocatalytic carbon dioxide reduction leading to the production of carbon rich products at low applied potentials with high product selectivity.


2020 ◽  
Vol 3 (7) ◽  
pp. 6670-6677
Author(s):  
Joo Yeon Kim ◽  
C. Hyun Ryu ◽  
Jeong Heon Lee ◽  
Amol U. Pawar ◽  
Woo-Dong Jang ◽  
...  

2002 ◽  
Vol 16 (3) ◽  
pp. 593-600 ◽  
Author(s):  
Siauw Ng ◽  
Jinsheng Wang ◽  
Yuxia Zhu ◽  
Ligang Zheng ◽  
Fuchen Ding ◽  
...  

ACS Catalysis ◽  
2017 ◽  
Vol 7 (11) ◽  
pp. 7704-7708 ◽  
Author(s):  
Michael J. Kinghorn ◽  
Gabriel A. Valdivia-Berroeta ◽  
Donalee R. Chantry ◽  
Mason S. Smith ◽  
Chloe C. Ence ◽  
...  

2005 ◽  
Vol 219 (7-2005) ◽  
pp. 905-920 ◽  
Author(s):  
Vasudev N. Shetti ◽  
D. Srinivas ◽  
P. Ratnasamy

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