01790nas a2200229   4500008004100000022001400041245009600055210006900151260006900220300001000289490000800299520094800307653004901255653002101304653001601325653001201341100002301353700002501376700002101401700001701422856012101439       2016                        eng d  a0022-328X00aExploring activity differences between the hydroformylation catalysts: Insights from theory0 aExploring activity differences between the hydroformylation cata  aPO BOX 564, 1001 LAUSANNE, SWITZERLANDbELSEVIER SCIENCE SAcJAN  a30-410 v8013 a<p>Hydroformylation catalysis is the most important homogeneous catalysis process of the current day. The current computational investigation aims to understand the nature of the hydroformylation process when monodentate ligands are employed. The complete catalytic cycle for different monodentate ligands bound to the rhodium center has been studied with full quantum chemical calculations, with density functional theory (DFT). To the best of our knowledge, this is the first systematic investigation of the relative free energy surfaces for mono-coordinate monodentate and bi-coordinated monodentate ligands in hydroformylation catalysis. The results indicate that the barriers are lower for the mono-coordinate monodentate species in comparison to the bi-coordinate monodentate, for all the ligand cases studied, indicating higher activity for the mono-coordinate monodentate active species. (C) 2015 Elsevier B.V. All rights reserved.</p>10aDensity functional theory (DFT) calculations10aHydroformylation10aMonodentate10aRhodium1 aDangat, Yuvraj, B.1 aRizvi, Masood, Ahmad1 aPandey, Pippalad1 aVanka, Kumar  uhttps://library.ncl.res.in/content/exploring-activity-differences-between-hydroformylation-catalysts-insights-theory02224nas a2200253   4500008004100000022001400041245010100055210006900156260000800225300001100233490000800244520136700252653002401619653003201643653002201675653002901697653002101726653001801747100002101765700001901786700002401805700001701829856012401846       2023                        eng d  a0022-328X00aComputational insights into the iron-catalyze d magnesium-me diate d hydroformylation of alkynes0 aComputational insights into the ironcatalyze d magnesiumme diate  cFEB  a1226210 v9863 a<p>
	Iron is one of the most abundant transition metals in the earth's crust. It has attracted a lot of attention due to its low toxicity, bio-compatibility, and high natural abundance. Iron-catalyzed hydroamination, hydroalkoxylation, hydrocarboxylation, hydrosilylation, hydroboration, hydrophosphination, hydromagnesiation, and carbonylation reactions have therefore been developed over the past decades. However, despite many experimental and theoretical studies, a complete mechanistic understanding of iron-catalyzed hydrofunctionalisation at the molecular level has not yet been achieved. In this work, through density functional theory (DFT) calculations, we have shown the most feasible path for the hydroformylation of alkynes for an experimentally studied system. We have looked at the iron salt as a precatalyst without any external donor ligand, and the calculations revealed that hydrometalation followed by beta-hydride elimination was favorable over the direct migration of the beta-hydrogen to carbon. Furthermore, our calculations show that the solvent plays an important role in the hydromagnesiation reaction. Furthermore, we have employed an explicit solvent model, where the attachment of one molecule of solvent to the iron center was seen to stabilize the transition states significantly.(c) 2023 Elsevier B.V. All rights reserved.</p>
10aComputational study10aEthylene Assisted Catalysis10aEtMgBr Assistance10aExplicit Role of Solvent10aHydroformylation10aIron Catalyst1 aSharma, Himanshu1 aTewari, Tanuja1 aChikkali, Samir, H.1 aVanka, Kumar  uhttps://library.ncl.res.in/content/computational-insights-iron-catalyze-d-magnesium-me-diate-d-hydroformylation-alkynes