DFT Calculations Investigate Competing Pathways to Form Dimeric Neopentylpalladium(II) Amido Complexes: The Critical Importance of Dispersion

2020 ◽  
Vol 124 (42) ◽  
pp. 8798-8805
Author(s):  
Quan Jiang ◽  
Thomas R. Cundari
Keyword(s):  
Dft Calculations ◽  
Critical Importance ◽  
Amido Complexes ◽  
Competing Pathways

scholarly journals DFT Calculations Investigate Competing Pathways to Form Dimeric Neopentylpalladium(II) Amido Complexes

2020 ◽  
Author(s):  
Quan Jiang ◽  
David Matthew Peacock ◽  
John Hartwig ◽  
Thomas Cundari
Keyword(s):  
Dft Calculations ◽  
Electron Density ◽  
Computational Methods ◽  
Side Reaction ◽  
Critical Importance ◽  
Dispersion Interactions ◽  
Frontier Orbitals ◽  
Amido Complexes ◽  
Dative Bond ◽  
Competing Pathways

Computational methods were utilized to study the formation of a dimeric neopentylpalladium(II) amido complex (D). The dimeric core of D contains asymmetric bridging of the anilide groups. Electron density analyses indicate that each palladium center of D forms a dative bond to the nitrogen trans to the coordinated phosphine, while the bond to the nitrogen cis to the phosphine lies closer to the covalent regime. Analysis of the structure of D was corroborated by study of the frontier orbitals and the energetics of dimerization. D was likely generated by the monomers with cis P,N configuration rather than those with trans P,N configuration, which is an important side reaction that inhibits the desired C–N bond coupling. Calculations further revealed the critical importance of dispersion interactions upon dimerization and suggested one possible dimeric isomer Q.<br>

scholarly journals DFT Calculations Investigate Competing Pathways to Form Dimeric Neopentylpalladium(II) Amido Complexes

2020 ◽  
Author(s):  
Quan Jiang ◽  
Thomas Cundari
Keyword(s):  
Dft Calculations ◽  
Electron Density ◽  
Computational Methods ◽  
Side Reaction ◽  
Critical Importance ◽  
Dispersion Interactions ◽  
Frontier Orbitals ◽  
Amido Complexes ◽  
Dative Bond ◽  
Competing Pathways

Computational methods were utilized to study the formation of a dimeric neopentylpalladium(II) amido complex (D). The dimeric core of D contains asymmetric bridging of the anilide groups. Electron density analyses indicate that each palladium center of D forms a dative bond to the nitrogen trans to the coordinated phosphine, while the bond to the nitrogen cis to the phosphine lies closer to the covalent regime. Analysis of the structure of D was corroborated by study of the frontier orbitals and the energetics of dimerization. D was likely generated by the monomers with cis P,N configuration rather than those with trans P,N configuration, which is an important side reaction that inhibits the desired C–N bond coupling. Calculations further revealed the critical importance of dispersion interactions upon dimerization and suggested one possible dimeric isomer Q.<br>

DFT Calculations Investigate Competing Pathways to Form Dimeric Neopentylpalladium(II) Amido Complexes

2020 ◽  
Author(s):  
Quan Jiang ◽  
Thomas Cundari
Keyword(s):  
Dft Calculations ◽  
Electron Density ◽  
Computational Methods ◽  
Side Reaction ◽  
Critical Importance ◽  
Dispersion Interactions ◽  
Frontier Orbitals ◽  
Amido Complexes ◽  
Dative Bond ◽  
Competing Pathways

Computational methods were utilized to study the formation of a dimeric neopentylpalladium(II) amido complex (D). The dimeric core of D contains asymmetric bridging of the anilide groups. Electron density analyses indicate that each palladium center of D forms a dative bond to the nitrogen trans to the coordinated phosphine, while the bond to the nitrogen cis to the phosphine lies closer to the covalent regime. Analysis of the structure of D was corroborated by study of the frontier orbitals and the energetics of dimerization. D was likely generated by the monomers with cis P,N configuration rather than those with trans P,N configuration, which is an important side reaction that inhibits the desired C–N bond coupling. Calculations further revealed the critical importance of dispersion interactions upon dimerization and suggested one possible dimeric isomer Q.<br>

scholarly journals On the reactivity of anodically generated trifluoromethyl radicals toward aryl alkynes in organic/aqueous media

2019 ◽  
Vol 17 (14) ◽  
pp. 3529-3537 ◽  
Author(s):  
Wolfgang Jud ◽  
C. Oliver Kappe ◽  
David Cantillo
Keyword(s):  
Dft Calculations ◽  
Aqueous Media ◽  
Competing Pathways ◽  
Aryl Alkynes

Two competing pathways have been experimentally observed and the selectivity has been explained by means of DFT calculations.

Structure elucidation of a proton-deficient natural product using LR-HSQMBC supported by DFT calculations

Planta Medica ◽  
2015 ◽  
Vol 81 (11) ◽  
Author(s):  
J Saurí ◽  
STS Chan ◽  
AV Buevich ◽  
KR Gustafson ◽  
RT Williamson ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Natural Product ◽  
Structure Elucidation

Next-Generation Sequencing of Sporadic Schwannomas Reveals Critical Importance of NF2 Alteration

2016 ◽  
Vol 77 (S 01) ◽  
Author(s):  
Pankaj Agarwalla ◽  
Wenya Bi ◽  
William Gibson ◽  
Shakti Ramkissoon ◽  
Steven Schumacher ◽  
...  
Keyword(s):  
Next Generation Sequencing ◽  
Next Generation ◽  
Critical Importance ◽  
Generation Sequencing
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