Université de Fribourg

Catalytic hydrogenation using abnormal N-heterocyclic carbene palladium complexes: catalytic scope and mechanistic insights

Heckenroth, Marion ; Khlebnikov, Vsevolod ; Neels, Antonia ; Schurtenberger, Peter ; Albrecht, Martin

In: ChemCatChem, 2011, vol. 3, no. 1, p. 167-173

Palladium complexes containing abnormally bound C4-bound dicarbene ligands have been exploited for catalytic alkene hydrogenation. Comparison to normally C2-bound homologues indicates that the carbene bonding mode critically influences the catalytic activity. Good catalytic performance in the hydrogenation of cis-disubstituted olefins and non-isomerizable terminal olefins under mild...

Université de Fribourg

Chelating NHC ruthenium(II) complexes as robust homogeneous hydrogenation catalysts

Gandolfi, Claudio ; Heckenroth, Marion ; Neels, Antonia ; Laurenczy, Gbor ; Albrecht, Martin

In: Organometallics, 2009, vol. 28, no. 17, p. 5112–5121

A series of ruthenium(II) complexes have been prepared by using bidentate chelating N-heterocyclic carbene (NHC) ligands that feature different donor groups E (E = olefin, thioether, carboxylate, and NHC). Rigid coordination of all donor sites was concluded from NMR spectroscopy, and the electronic impact of the donor group was evaluated by electrochemical analyses. The chelating donor group had...

Université de Fribourg

On the electronic impact of abnormal C4-bonding in N-heterocyclic carbene complexes

Heckenroth, Marion ; Neels, Antonia ; Garnier, Michael G. ; Aebi, Philipp ; Ehlers, Andreas W. ; Albrecht, Martin

In: Chemistry - A European Journal, 2009///doi: 10.1002/chem.200900249

Sterically similar palladium dicarbene complexes have been synthesized that comprise permethylated dicarbene ligands which bind the metal center either in a normal coordination mode via C2 or abnormally via C4. Due to the strong structural analogy of the complexes, differences in reactivity patterns may be attributed to the distinct electronic impact of normal versus abnormal carbene bonding,...

Université de Neuchâtel

Synthesis and structural analysis of palladium biscarbene complexes derived from bisimidazolium ligand precursors

Heckenroth, Marion ; Neels, Antonia ; Stoeckli-Evans, Helen ; Albrecht, Martin

In: Inorganica Chimica Acta, 2006, vol. 359, no. 6, p. 316-330

The palladation of potentially chelating bisimidazolium ligand precursors with palladium acetate gives bridging bimetallic, chelating monometallic, and homoleptic tetracarbene complexes. The coordination mode of the biscarbene ligand has been identified by spectroscopic analysis and crystallographic characterization of representative complexes, including the first example of a biscarbene A-frame...

Université de Fribourg

Palladation of diimidazolium salts at the C4 position: access to remarkably electron-rich palladium(II) centers

Heckenroth, Marion ; Kluser, Evelyne ; Neels, Antonia ; Albrecht, Martin

In: Dalton Transactions, 2008, p. 6242 - 6249

Palladation of C2-protected diimidazolium salts with Pd(OAc)₂ afforded complexes comprising C4-bound N-heterocyclic dicarbene ligands. The reactivity of these complexes towards Lewis acids (AgBF₄, AgOAc) and Brønsted acids (H₂SO₄, H₃PO₄, HOAc) revealed that abnormal C4 bonding of the carbenes markedly increases the nucleophilicity of the coordinated palladium center as compared to C2...

Université de Fribourg

Palladium complexes comprising C(4)-bound diimidazolylidene carbenes

Heckenroth, Marion ; Albrecht, Martin

In: Chimia, 2008, vol. 62, no. 4, p. 253-255

Imidazolium-derived palladium dicarbene complexes have been synthesized which feature either normal C(2) carbene bonding or abnormal C(4) bonding. Comparison of the reactivity of these complexes, in particular towards Lewis acids (H⁺, Ag⁺), indicate consistently that C(4)-bound carbenes are stronger donors than their C(2)-bound analogs. As a consequence of this electronic impact, palladium...

Université de Fribourg

Synthesis and structural analysis of palladium biscarbene complexes derived from bisimidazolium ligand precursors

Heckenroth, Marion ; Neels, Antonia ; Stoeckli-Evans, Helen ; Albrecht, Martin

In: Inorganica Chimica Acta, 2006, vol. 359, no. 6, p. 1929-1938

The palladation of potentially chelating bisimidazolium ligand precursors with palladium acetate gives bridging bimetallic, chelating monometallic, and homoleptic tetracarbene complexes. The coordination mode of the biscarbene ligand has been identified by spectroscopic analysis and crystallographic characterization of representative complexes, including the first example of a biscarbene A-frame...