0000000001315006
AUTHOR
Agustí Lledós
Influence of the Nature of the Ligand on Dirhodium(II) Carbene Species: A Theoretical Analysis
The influence of three prototypic families of bridging ligands (carboxylate, carboxamidate, and ortho-metalated arylphosphines) on the electronic structure of dirhodium(II) carbene complexes was theoretically analyzed. The calculations indicated that the electron donation of the ligand to the Rh atom, rather than the chelating ability or the metal−ligand orbital mixing, was responsible for tuning carbene charge via back-donation, which can influence the reactivity and selectivity of the dirhodium complexes in catalytic carbene transfer reactions.
Experimental and Computational Studies of Hydrogen Bonding and Proton Transfer to [Cp*Fe(dppe)H]
The present contribution reports experimental and computational investigations of the interaction between [Cp*Fe(dppe)H] and different proton donors (HA). The focus is on the structure of the proton transfer intermediates and on the potential energy surface of the proton transfer leading to the dihydrogen complex [Cp*Fe(dppe)(H2)]+. With p-nitrophenol (PNP) a UV/Visible study provides evidence of the formation of the ion-pair stabilized by a hydrogen bond between the nonclassical cation [Cp*Fe(dppe)(H2)]+ and the homoconjugated anion ([AHA]-). With trifluoroacetic acid (TFA), the hydrogen-bonded ion pair containing the simple conjugate base (A-) in equilibrium with the free ions is observed…
Gold(I)-catalyzed intermolecular oxyarylation of alkynes: unexpected regiochemistry in the alkylation of arenes.
The reaction between acetylenes and sulfoxides, studied as a test case for gold-catalyzed intermolecular addition, provides the oxyarylation compounds 3 in good yields. Unpredictably, in all cases a single regioisomer arising from the electrophilic aromatic alkylation at the position adjacent to the sulfur atom is obtained instead of the expected Friedel−Crafts regioisomer. A new concerted mechanism based on DFT calculations is proposed to account for the products in this intermolecular gold(I)-catalyzed reaction.
On the Road to MM′X Polymers: Redox Properties of Heterometallic Ni···Pt Paddlewheel Complexes
On the quest of heterometallic mixed-valence MM'X chains, we have prepared two stable discrete bimetallic compounds: the reduced (PPN)[ClNi(μ-OSCPh)4Pt] (PPN = bis(triphenylphosphine)iminium; OSCPh = benzothiocarboxylato) and the oxidized [(H2O)Ni(μ-OSCPh)4PtCl] species. The role of the aqua and chlorido axial ligands is crucial to facilitate oxidation of the {Ni(μ-OSCPh)4Pt} core. Experimental and theoretical analyses indicate that a NiPt-Cl/Cl-NiPt isomerization process occurs in the oxidized species. The electronic structure of the reduced system shows two unpaired electrons, one located in a d(x(2)-y(2)) orbital of the Ni(II) ion and a second in the antibonding d(z(2)-dz(2)) combination…
ChemInform Abstract: Gold(I)-Catalyzed Intermolecular Oxyarylation of Alkynes: Unexpected Regiochemistry in the Alkylation of Arenes.
The reaction between acetylenes and sulfoxides, studied as a test case for gold-catalyzed intermolecular addition, provides the oxyarylation compounds 3 in good yields. Unpredictably, in all cases a single regioisomer arising from the electrophilic aromatic alkylation at the position adjacent to the sulfur atom is obtained instead of the expected Friedel−Crafts regioisomer. A new concerted mechanism based on DFT calculations is proposed to account for the products in this intermolecular gold(I)-catalyzed reaction.
CCDC 1013364: Experimental Crystal Structure Determination
Related Article: Marcello Gennari, Gonzalo Givaja, Oscar Castillo, Laura Hermosilla, Carlos J. Gómez-García, Carole Duboc, Agustí Lledós, Ruben Mas-Ballesté, and Felix Zamora|2014|Inorg.Chem.|53|10553|doi:10.1021/ic501659x
CCDC 1013365: Experimental Crystal Structure Determination
Related Article: Marcello Gennari, Gonzalo Givaja, Oscar Castillo, Laura Hermosilla, Carlos J. Gómez-García, Carole Duboc, Agustí Lledós, Ruben Mas-Ballesté, and Felix Zamora|2014|Inorg.Chem.|53|10553|doi:10.1021/ic501659x