Abstract
The preparation of a series of rhodium(I) complexes coordinated by various electronically tuneable Fischer carbene (FC) ligands, is reported. The Rh(I) metal complexes’ electronic properties could readily be modulated by variation of a p-N,N-dimethylaniline moiety with a ruthenocenyl substituent, or alternatively, substituting the carbene O-heteroatom for an amino-group. The electronic properties of the complexes were evaluated, and it was determined from the Tolman electronic parameters that the donor-ability of the FC ligands are comparable to N-heterocyclic carbenes. Furthermore, the facile control of the electronic properties of the complexes was demonstrated by mild oxidation of a ferrocenyl aminocarbene rhodium(I) complex, yielding the corresponding ferrocenium rhodium(I) complex cation. Finally, the complexes were evaluated as catalyst precursors for the hydroformylation of 1-octene.
Highlights
The use of mono-heteroatom-stabilized Fischer carbene ligands in catalytic applications are still predominantly unexplored, the exploitation of Fischer carbene complexes (FCCs) in photophysical, optical and sensing applications are on the rise [1]
This dearth in homogeneous catalysis application can mostly be ascribed to the challenges related to the preparation of FCCs of the late transition metals [2], whereby self-dimerisation of the carbene ligand to the corresponding olefin is observed during transmetallation reactions from the group 6 metal FCC precursors [3]
We have previously demonstrated the stability of the oxidized ferrocenium ethoxycarbene ligand, and could isolate the first examples of the radical cations of such ferrocenyl FCCs [13]
Summary
The use of mono-heteroatom-stabilized Fischer carbene ligands in catalytic applications are still predominantly unexplored, the exploitation of Fischer carbene complexes (FCCs) in photophysical, optical and sensing applications are on the rise [1]. This dearth in homogeneous catalysis application can mostly be ascribed to the challenges related to the preparation of FCCs of the late transition metals [2], whereby self-dimerisation of the carbene ligand to the corresponding olefin is observed during transmetallation reactions from the group 6 metal FCC precursors [3]. Synthesis of 1e3 via transmetallation from group 6 FCCs. * Complex 3 has been previously reported [4a]
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