02224nas 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-alkynes02091nas a2200241   4500008004100000022001400041245010400055210006900159260000900228490000700237520124700244653001701491653003501508653002901543653003301572653001801605100001701623700001701640700001901657700002401676700002401700856012501724       2023                        eng d  a0947-653900aIron-catalyzed alkoxylation, dehydrogenative-polymerization and tandem hydrosilylative-alkoxylation0 aIroncatalyzed alkoxylation dehydrogenativepolymerization and tan  cAUG 0 v293 a<p>Alkoxylation, hydrosilylative-alkoxylation, and dehydrogenative-polymerization are some of the most widely used transformations in synthetic chemistry. However, these transformations are traditionally catalyzed by precious, and rare late-transition metals. Presented here is a molecularly defined iron complex that catalyzes alkoxylation, tandem hydrosilylative-alkoxylation, and dehydrogenative polymerization of silanes under mild conditions. The iron complex [Fe(CO)(4)(H)(SiPh3)] 1 catalyzes a direct Si-O coupling reaction between an array of silanes and alcohols to produce desired alkoxysilanes in excellent yield, with H-2 as the only byproduct. The iron catalyst tolerates various functional groups and provides access to 20 alkoxysilanes, including essential molecules such as &amp; beta;-citronellol and cholesterol. Further, complex 1 catalyzes the polymerization of renewable diol and silane monomer to produce a renewable and degradable poly(isosorbide-silyl ether). Remarkably, complex 1 catalyzes a tandem hydrosilylative-alkoxylation of alkynes under mild conditions to yield unsaturated silyl ethers. The synthetic utility has been demonstrated by gram-scale alkoxylation and hydrosilylative-alkoxylation reactions.</p>
10aalkoxylation10adehydrogenative polymerization10aearth abundant catalysts10ahydrosilylative-alkoxylation10aIron Catalyst1 aSen, Anirban1 aKumar, Rohit1 aTewari, Tanuja1 aGonnade, Rajesh, G.1 aChikkali, Samir, H.  uhttps://library.ncl.res.in/content/iron-catalyzed-alkoxylation-dehydrogenative-polymerization-and-tandem-hydrosilylative