Dataset Information

Hierarchy of Commonly Used DFT Methods for Predicting the Thermochemistry of Rh-Mediated Chemical Transformations.

ABSTRACT: The accuracy and reliability of 17 commonly used density functionals in conjunction with Poisson-Boltzmann finite solvation model were gauged for predicting the free energy of Rh(I)- and Rh(III)-mediated chemical transformations such as ligand exchange, hydride elimination, dihydrogen elimination, chloride affinity, and silyl hydride bond activation reactions. In total, six Rh-mediated reactions were examined, and the computed density functional theory results were then subjected to comparison with the experimentally reported values. For reaction A, involving replacement of N2 with ?2-H2 over Rh(I), MPWB1K-D3, B3PW91, B3LYP, and BHandHYLP emerged to be the best functionals of all the tested methods in terms of their deviations ?2 kcal mol-1 from experimental data. For reaction B, in which exchange of ?2-C2H4 with N2 over Rh(I) takes place, MPWB1K-D3 and M06-2X-D3 functionals performed the best, while as for reaction C (hydride elimination reaction in Rh(III) complex), it is PBE functional that showed impressive performance. Similarly, for reaction D (H2 elimination reaction in Rh(III) complex), PBE0-D3 and PBE-D3 showed exceptional results compared to other functionals. For reaction E (H2O/Cl- exchange), the PBE0 again shows impressive performance as compared to other functionals. For reaction F (Si-H activation), M06-2X-D3, PBE0-D3, and MPWB1K-D3 functionals are undoubtedly the best functionals. Overall, PBE0-D3 and MPWB1K-D3 functionals were impressive in all cases with lowest mean unsigned errors (3.2 and 3.4 kcal mol-1, respectively) with respect to experimental Gibbs free energies. Thus, these two functionals are recommended for studying Rh-mediated chemical transformations.

SUBMITTER: Shiekh BA

PROVIDER: S-EPMC6761679 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Hierarchy of Commonly Used DFT Methods for Predicting the Thermochemistry of Rh-Mediated Chemical Transformations.

Shiekh Bilal Ahmad BA

ACS omega 20190913 13

The accuracy and reliability of 17 commonly used density functionals in conjunction with Poisson-Boltzmann finite solvation model were gauged for predicting the free energy of Rh(I)- and Rh(III)-mediated chemical transformations such as ligand exchange, hydride elimination, dihydrogen elimination, chloride affinity, and silyl hydride bond activation reactions. In total, six Rh-mediated reactions were examined, and the computed density functional theory results were then subjected to comparison w ...[more]

PMID: 31572844

Similar Datasets

Project description:BackgroundAnopheles gambiae M and S molecular forms, the major malaria vectors in the Afro-tropical region, are ongoing a process of ecological diversification and adaptive lineage splitting, which is affecting malaria transmission and vector control strategies in West Africa. These two incipient species are defined on the basis of single nucleotide differences in the IGS and ITS regions of multicopy rDNA located on the X-chromosome. A number of PCR and PCR-RFLP approaches based on form-specific SNPs in the IGS region are used for M and S identification. Moreover, a PCR-method to detect the M-specific insertion of a short interspersed transposable element (SINE200) has recently been introduced as an alternative identification approach. However, a large-scale comparative analysis of four widely used PCR or PCR-RFLP genotyping methods for M and S identification was never carried out to evaluate whether they could be used interchangeably, as commonly assumed.ResultsThe genotyping of more than 400 A. gambiae specimens from nine African countries, and the sequencing of the IGS-amplicon of 115 of them, highlighted discrepancies among results obtained by the different approaches due to different kinds of biases, which may result in an overestimation of MS putative hybrids, as follows: i) incorrect match of M and S specific primers used in the allele specific-PCR approach; ii) presence of polymorphisms in the recognition sequence of restriction enzymes used in the PCR-RFLP approaches; iii) incomplete cleavage during the restriction reactions; iv) presence of different copy numbers of M and S-specific IGS-arrays in single individuals in areas of secondary contact between the two forms.ConclusionsThe results reveal that the PCR and PCR-RFLP approaches most commonly utilized to identify A. gambiae M and S forms are not fully interchangeable as usually assumed, and highlight limits of the actual definition of the two molecular forms, which might not fully correspond to the two A. gambiae incipient species in their entire geographical range. These limits are discussed and operational suggestions on the choice of the most convenient method for large-scale M- and S-form identification are provided, also taking into consideration technical aspects related to the epidemiological characteristics of different study areas.

Dataset Information

Hierarchy of Commonly Used DFT Methods for Predicting the Thermochemistry of Rh-Mediated Chemical Transformations.

Publications

Hierarchy of Commonly Used DFT Methods for Predicting the Thermochemistry of Rh-Mediated Chemical Transformations.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets