A Holy Grail in Chemistry: Computational Catalyst Design: Feasible or Fiction?

Poree, Carl; Schoenebeck, Franziska

doi:10.1021/acs.accounts.6b00606

Cited by 135 publications

(134 citation statements)

References 14 publications

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“…Significant synthetic efforts to provide ligands with tailored electronic and steric binding pockets for the metal fragment have adapted organometallics and coordination compounds to the specific requirements of various catalytic processes . When a ligand is selected, the coordination environment around the metal ion as well as the rate and selectivity of the resulting complex within a given transformation are determined . Metal–ligand cooperation phenomena or metal‐induced permanent modifications of the ligand structure affect the metal coordination sphere.…”

Section: Introductionmentioning

confidence: 99%

Benzoimidazole‐Pyridylamido Zirconium and Hafnium Alkyl Complexes as Homogeneous Catalysts for Tandem Carbon Dioxide Hydrosilylation to Methane

et al. 2018

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Neutral ZrIV and HfIV alkyl/amido complexes stabilized by a tridentate N ligand that contains a “rolling” heterodentate benzoimidazole fragment have been prepared and characterized. The ultimate nature of the ligand denticity, the electronic properties of the ligand binding pocket and the metal coordination environment are controlled by the protection/deprotection of the benzoimidazole NH group. The metal precursor used [MIV(Bn)4 or MIV(NMe2)4] also has an influence on the final coordination sphere of the complex; indeed, a permanent central pyridine dearomatization occurs in the presence of dimethylamido ancillary groups. DFT calculations on the real system have been used to elucidate the mechanism. Selected alkyl species from this series have been scrutinized for the tandem hydrosilylation of CO2 to CH4 in combination with the strong Lewis acid B(C6F5)3 using a variety of hydrosilanes. A positive effect of the hardness modification of the ligand donor atom set is observed in the catalytic outcomes. Indeed, κ3{N−,N,N−}ZrIV(Bn)2 catalyzes the process to methane selectively with a turnover frequency as high as 272 h−1 (at 96 % substrate conversion) almost twice as much as that claimed for the benchmark κ3{O−,O,O−}ZrIV(Bn)2 complex under similar experimental conditions.

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Section: Introductionmentioning

confidence: 99%

Benzoimidazole‐Pyridylamido Zirconium and Hafnium Alkyl Complexes as Homogeneous Catalysts for Tandem Carbon Dioxide Hydrosilylation to Methane

et al. 2018

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“…[21,22] To gain insight into the proposed Pd 0/II decarbonylative cross-coupling platform, density functional theory (DFT) calculations were performed elucidating the mechanistic details and origins of chemoselectivity of the CÀOb ond activation (Figure 3). [21,22] To gain insight into the proposed Pd 0/II decarbonylative cross-coupling platform, density functional theory (DFT) calculations were performed elucidating the mechanistic details and origins of chemoselectivity of the CÀOb ond activation (Figure 3).…”

mentioning

confidence: 99%

Palladium‐Catalyzed Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction Selectivity by Computation

Liu,

Ji,

Hong

et al. 2018

Angew Chem Int Ed

104

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Decarbonylative borylation of carboxylic acids is reported. Carbon electrophiles are generated directly after reagent-enabled decarbonylation of the in situ accessible sterically-hindered acyl derivative of ac arboxylic acid under catalyst controlled conditions.T he scope and the potential impact of this method are demonstrated in the selective borylation of av ariety of aromatics (> 50 examples). This strategy was used in the late-stage derivatization of pharmaceuticals and natural products.C omputations reveal the mechanistic details of the unprecedented CÀObond activation of carboxylic acids.B ycircumventing the challenging decarboxylation, this strategy provides ag eneral synthetic platform to access arylpalladium species for aw ide arrayo fb ond formations from abundant carboxylica cids.T he study shows ap owerfulc ombination of experiment and computation to predict decarbonylation selectivity.

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“…Over the last two decades, computational chemistry has evolved into a key tool for unraveling the mechanistic intricacies of TM‐catalyzed systems . Currently, due to major advances in the development of theoretical methods, software, and hardware, it is possible to resolve quantum mechanics (QM) systems at a reasonable timescale.…”

Section: Computational Tools For Rational Design In Homogeneous Catalmentioning

confidence: 99%

Sustainable Knowledge‐Driven Approaches in Transition‐Metal‐Catalyzed Transformations

et al. 2019

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A Holy Grail in Chemistry: Computational Catalyst Design: Feasible or Fiction?

Cited by 135 publications

References 14 publications

Benzoimidazole‐Pyridylamido Zirconium and Hafnium Alkyl Complexes as Homogeneous Catalysts for Tandem Carbon Dioxide Hydrosilylation to Methane

Benzoimidazole‐Pyridylamido Zirconium and Hafnium Alkyl Complexes as Homogeneous Catalysts for Tandem Carbon Dioxide Hydrosilylation to Methane

Palladium‐Catalyzed Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction Selectivity by Computation

Sustainable Knowledge‐Driven Approaches in Transition‐Metal‐Catalyzed Transformations

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