Unusual Rearrangement of an N-Donor-Functionalized N-Heterocyclic Carbene Ligand on Group 8 Metals

Qiuming Liang; Andrew Salmon; Patrick Jinhyung Kim; Linfan Yan; Datong Song

doi:10.1021/jacs.7b13097

Unusual Rearrangement of an N-Donor-Functionalized N-Heterocyclic Carbene Ligand on Group 8 Metals

J Am Chem Soc. 2018 Jan 31;140(4):1263-1266. doi: 10.1021/jacs.7b13097. Epub 2018 Jan 16.

Authors

Qiuming Liang¹, Andrew Salmon¹, Patrick Jinhyung Kim¹, Linfan Yan¹, Datong Song¹

Affiliation

¹ Davenport Chemical Research Laboratories, Department of Chemistry, University of Toronto , 80 St. George Street, Toronto, Ontario M5S 3H6, Canada.

PMID: 29320184
DOI: 10.1021/jacs.7b13097

Abstract

We report an unexpected rearrangement of a deprotonated picolyl-functionalized N-heterocyclic carbene (NHC) ligand from N,C-chelate to N,N-chelate in three-legged piano-stool Fe(II) and Ru(II) complexes. The reaction mechanism has been explored for one of the Fe(II) complexes. Experimental and computational studies suggest an unusual intermediate featuring a four-membered chelate ring, where the NHC and the α-carbon of one of the N-substituents coordinate to the Fe(II) center. A possible Fe-alkylidene intermediate has also been predicted by computations.

Publication types

Research Support, Non-U.S. Gov't