Electrophilic Ln(III) cations protected by C-F → Ln interactions and their coordination chemistry with weak σ- and π-donors

Haolin Yin; Andrew J Lewis; Patrick Carroll; Eric J Schelter

doi:10.1021/ic401130e

Electrophilic Ln(III) cations protected by C-F → Ln interactions and their coordination chemistry with weak σ- and π-donors

Inorg Chem. 2013 Jul 15;52(14):8234-43. doi: 10.1021/ic401130e. Epub 2013 Jun 26.

Authors

Haolin Yin¹, Andrew J Lewis, Patrick Carroll, Eric J Schelter

Affiliation

¹ P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34 Street, Philadelphia, Pennsylvania 19104, USA.

PMID: 23802923
DOI: 10.1021/ic401130e

Abstract

A homoleptic cerium(III) amide complex, Ce(NPh(F)2)3 (1-Ce) (Ph(F) = pentafluorophenyl), in an unusual pseudo-trigonal planar geometry featuring six C-F → Ce interactions was prepared. The C-F → Ln interactions in solution were evident by comparison of the (19)F NMR shifts for the paramagnetic 1-Ce with those of the 4f(0) lanthanum(III) analogue. Coordination of weak σ- and π-donors, including ethers and neutral arene molecules, was achieved by the reversible displacement of the weak C-F → Ce interactions. Computational studies on Ce(NPh(F)2)3 and Ce(NPh(F)2)3(η(6)-C6H3Me3) provide information on the F → Ce interactions and Ce-η(6)-arene bonding.