Federica Bertini

Geminal phosphorus/aluminum-based frustrated lewis pairs: C−H versus C≡C activation and CO2 fixation.

Catch it! Geminal phosphorus/aluminum-based frustrated Lewis pairs (FLPs) are easily obtained by hydroalumination of alkynylphosphines. These FLPs can activate terminal acetylenes by two competitive pathways, which were analyzed by DFT calculations, and they can bind carbon dioxide reversibly. Therefore, alongside polyfluorinated boranes, alanes are also ideal Lewis acids for FLP chemistry.

Preorganized frustrated Lewis pairs.

Geminal frustrated Lewis pairs (FLPs) are expected to exhibit increased reactivity when the donor and acceptor sites are perfectly aligned. This is shown for reactions of the nonfluorinated FLP tBu(2)PCH(2)BPh(2) with H(2), CO(2), and isocyanates and supported computationally.

An active, stable and recyclable Ru(II) tetraphosphine-based catalytic system for hydrogen production by selective formic acid dehydrogenation

Well-defined and in situ made Ru(II) complexes of the linear tetraphosphine ligand meso-1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane (tetraphos-1, P4) proved to be effective catalysts for selective formic acid dehydrogenation with good yields and TONs in the presence of an added amine, both under batch and continuous feed experimental conditions. The mechanism was studied by solution NMR and DFT calculations, highlighting the role of the trans-dihydrido complex [Ru(H)2(meso-P4)] as the active species in catalysis.

New Wind in Old Sails: Novel Applications of Triphos-based Transition Metal Complexes as Homogeneous Catalysts for Small Molecules and Renewables Activation.

Recent developments in the coordination chemistry and applications of Ru-triphos [triphos = 1,1,1-tris-(diphenylphosphinomethyl)ethane] systems are reviewed, highlighting their role as active and selective homogenous catalysts for small molecule activation, biomass conversions and in carbon dioxide utilization-related processes.

Hydrogen Activation in Water by Organometallic Complexes

Hydrogen has found important applications as reducing agent for chemical transformations and is nowadays considered as one of the most promising energy vectors able to fuel devices to produce electricity on demand (direct hydrogen fuel cells). Crucial to its application is the understanding at the molecular level of how hydrogen interacts with (transition) metals which are commonly used as catalysts to lower the energy barrier to split the H2 molecule into its components and allow transfer and reactivity. In this chapter, selected examples of hydrogen activation by water-soluble organometallic complexes are summarized.

Mechanistic Studies on NaHCO3 Hydrogenation and HCOOH Dehydrogenation Reactions Catalysed by a FeII Linear Tetraphosphine Complex

We present a theoretical extension of the previously published bicarbonate hydrogenation to formate and formic acid dehydrogenation catalysed by FeII complexes bearing the linear tetraphosphine ligand tetraphos-1. The hydrogenation reaction was found to proceed at the singlet surface with two competing pathways: A) H2 association to the Fe-H species followed by deprotonation to give a Fe(H)2 intermediate, which then reacts with CO2 to give formate. B) CO2 insertion into the Fe-H bond, followed by H2 association and subsequent deprotonation. B was found to be slightly preferred with an activation energy of 22.8 kcal mol-1 , compared to 25.3 for A. Further we have reassigned the Fe-H complex, as a Fe(H)(H2 ), which undergoes extremely rapid hydrogen exchange.