Transfer hydrogenation with abnormal dicarbene rhodium( iii ) complexes containing ancillary and modular poly-pyridine ligands

Farrell, Kevin; Melle, Philipp; Gossage, Robert A.; Müller-Bunz, Helge; Albrecht, Martin (2016). Transfer hydrogenation with abnormal dicarbene rhodium( iii ) complexes containing ancillary and modular poly-pyridine ligands. Dalton transactions, 45(11), pp. 4570-4579. Royal Society of Chemistry 10.1039/C5DT04656D

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Treatment of an abnormal dicarbene ligated rhodium(III) dimer with 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen) or 2,2′:6′,2′′-terpyridine (terpy) results in coordination of the N-donor ligands and concomitant cleavage of the dimeric structure. Depending on the denticity of the pyridyl ligand, this situation retains one (L = terpy) or two (L = bipy, phen) flexible sites for substrate coordination. In the case of the bipy complexes, modification of the electron density at Rh, without directly affecting the steric environment about the metal centre, was achieved by the incorporation of electron-donating or electron-withdrawing substituents on the bipy backbone. The dicarbene pyridyl complexes were active in transfer hydrogenation catalysis of benzophenone at 0.15 mol% catalyst loading in a iPrOH/KOH mixture. The catalysts displayed a strong characteristic colour change (yellow to purple) after activation which allowed for visual monitoring of the status of the reaction. The colour probe and the robustness of the active catalysts proved useful for catalyst recycling. The catalytic activity sustained over five consecutive substrate batch additions and gave a maximum overall turnover number of 3100.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Melle, Philipp and Albrecht, Martin

Subjects:

500 Science > 540 Chemistry

ISSN:

1477-9226

Publisher:

Royal Society of Chemistry

Language:

English

Submitter:

Eik Szee Goh Aschauer

Date Deposited:

19 Jan 2017 16:05

Last Modified:

19 Jan 2017 16:05

Publisher DOI:

10.1039/C5DT04656D

BORIS DOI:

10.7892/boris.93803

URI:

https://boris.unibe.ch/id/eprint/93803

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