@article {48283,
	title = {Computational insights into the iron-catalyze d magnesium-me diate d hydroformylation of alkynes},
	journal = {Journal of Organometallic Chemistry},
	volume = {986},
	year = {2023},
	month = {FEB},
	pages = {122621},
	type = {Article},
	abstract = {<p>
	Iron is one of the most abundant transition metals in the earth{\textquoteright}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>
},
	keywords = {Computational study, Ethylene Assisted Catalysis, EtMgBr Assistance, Explicit Role of Solvent, Hydroformylation, Iron Catalyst},
	issn = {0022-328X},
	doi = {10.1016/j.jorganchem.2023.122621},
	author = {Sharma, Himanshu and Tewari, Tanuja and Chikkali, Samir H. and Vanka, Kumar}
}
@article {48924,
	title = {Iron-catalyzed alkoxylation, dehydrogenative-polymerization and tandem hydrosilylative-alkoxylation},
	journal = {Chemistry- a european journal },
	volume = {29},
	year = {2023},
	month = {AUG },
	type = {Article},
	abstract = {<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>
},
	keywords = {alkoxylation, dehydrogenative polymerization, earth abundant catalysts, hydrosilylative-alkoxylation, Iron Catalyst},
	issn = {0947-6539},
	doi = {10.1002/chem.202301375},
	author = {Sen, Anirban and Kumar, Rohit and Tewari, Tanuja and Gonnade, Rajesh G. and Chikkali, Samir H.}
}
