Computational Mechanistic Study on Cp*Ir Complex-Mediated Acceptorless Alcohol Dehydrogenation: Bifunctional Hydrogen Transfer vs β-H Elimination

2011 ◽  
Vol 30 (8) ◽  
pp. 2349-2363 ◽  
Author(s):  
Haixia Li ◽  
Gang Lu ◽  
Jinliang Jiang ◽  
Fang Huang ◽  
Zhi-Xiang Wang
Keyword(s):  
Hydrogen Transfer ◽  
Mechanistic Study ◽  
Alcohol Dehydrogenation ◽  
Acceptorless Alcohol Dehydrogenation

Efficient Catalyst for Acceptorless Alcohol Dehydrogenation: Interplay of Theoretical and Experimental Studies

ACS Catalysis ◽  
2014 ◽  
Vol 4 (3) ◽  
pp. 1010-1020 ◽  
Author(s):  
Guixiang Zeng ◽  
Shigeyoshi Sakaki ◽  
Ken-ichi Fujita ◽  
Hayato Sano ◽  
Ryohei Yamaguchi
Keyword(s):  
Experimental Studies ◽  
Efficient Catalyst ◽  
Alcohol Dehydrogenation ◽  
Acceptorless Alcohol Dehydrogenation

scholarly journals Supported Cobalt Catalysts for Acceptorless Alcohol Dehydrogenation

ChemPlusChem ◽  
2020 ◽  
Vol 85 (6) ◽  
pp. 1315-1324 ◽  
Author(s):  
Kamila Kaźmierczak ◽  
Catherine Pinel ◽  
Stéphane Loridant ◽  
Michèle Besson ◽  
Carine Michel ◽  
...  
Keyword(s):  
Cobalt Catalysts ◽  
Supported Cobalt Catalysts ◽  
Alcohol Dehydrogenation ◽  
Acceptorless Alcohol Dehydrogenation

Synthesis of a Water-Soluble Ruthenium Complex and Its Catalytic Activity for Acceptorless Alcohol Dehydrogenation in Aqueous Medium

Synlett ◽  
2018 ◽  
Vol 29 (12) ◽  
pp. 1644-1648 ◽  
Author(s):  
Senthilkumar Muthaiah ◽  
Anita Bhatia
Keyword(s):  
Catalytic Activity ◽  
Aqueous Medium ◽  
Ruthenium Complex ◽  
Water Soluble ◽  
Catalytic Cycle ◽  
Secondary Alcohols ◽  
Atom Economy ◽  
Hydrogen Acceptor ◽  
Alcohol Dehydrogenation ◽  
Acceptorless Alcohol Dehydrogenation

The synthesis of a ruthenium complex bearing a PN-chelating ligand is described. The complex, in the presence of KOH, enabled the synthesis of ketones from secondary alcohols in the absence of a hydrogen acceptor in aqueous medium. This synthetic protocol, which uses water as the medium, is green and has a high atom economy as it avoids the use of an acceptor and produces hydrogen as the sole ­byproduct. Mechanistic investigations revealed that the catalytic cycle involves a phosphine dissociative pathway.

scholarly journals Bulky PNP Ligands Blocking Metal-Ligand Cooperation Allow for Isolation of Ru(0), and Lead to Catalytically Active Ru Complexes in Acceptorless Alcohol Dehydrogenation

2021 ◽  
Author(s):  
Shubham Deolka ◽  
Robert R. Fayzullin ◽  
Eugene Khaskin
Keyword(s):  
Ru Complex ◽  
Catalytically Active ◽  
Ru Complexes ◽  
Alcohol Dehydrogenation ◽  
Complex Chemistry ◽  
Acceptorless Alcohol Dehydrogenation ◽  
Cis And Trans ◽  
Metal Ligand

We synthesized two 4Me-PNP ligands which block metal-ligand cooperation (MLC) with the Ru center and compared their Ru complex chemistry to their two traditional analogues used in acceptorless alcohol dehydrogenation catalysis. The corresponding 4Me-PNP complexes, which do not undergo dearomatization upon addition of base, allowed us to obtain rare, albeit unstable, 16 electron mono CO Ru(0) complexes. Reactivity with CO and H<sub>2</sub> allows for stabilization and extensive characterization of bis CO Ru(0) 18 electron and Ru(II) cis and trans dihydride species that were also shown to be capable of C(sp<sup>2</sup>)-H activation. Reactivity and catalysis are contrasted to non-methylated Ru(II) species, showing that an MLC pathway is not necessary, with dramatic differences in outcomes during catalysis between <sup>i</sup>Pr and <sup>t</sup>Bu PNP complexes within each of the 4Me and non-methylated backbone PNP series being observed. Unusual intermediates are characterized in one of the new and one of the traditional complexes, and a common catalysis deactivation pathway was identified.

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