Unexpected formation of chiral pincer CNN nickel complexes with β-diketiminato type ligands via C-H activation: synthesis, properties, structures, and computational studies

Zhengliang Lu; Srinivas Abbina; Jared R Sabin; Victor N Nemykin; Guodong Du

doi:10.1021/ic3021904

Unexpected formation of chiral pincer CNN nickel complexes with β-diketiminato type ligands via C-H activation: synthesis, properties, structures, and computational studies

Inorg Chem. 2013 Feb 4;52(3):1454-65. doi: 10.1021/ic3021904. Epub 2013 Jan 15.

Authors

Zhengliang Lu¹, Srinivas Abbina, Jared R Sabin, Victor N Nemykin, Guodong Du

Affiliation

¹ Department of Chemistry, University of North Dakota, 151 Cornell Street Stop 9024, Grand Forks, North Dakota 58202, USA.

PMID: 23320602
DOI: 10.1021/ic3021904

Abstract

Reaction of lithiated chiral, unsymmetric β-diketimine type ligands HL(2a-e) containing oxazoline moiety (HL(2a-e) = 2-(2'-R(1)NH)-phenyl-4-R(2)-oxazoline) with trans-NiCl(Ph)(PPh(3))(2) afforded a series of new chiral CNN pincer type nickel complexes (3a-3e) via an unexpected cyclometalation at benzylic or aryl C-H positions. Single crystal X-ray diffraction analysis established the pincer coordination mode and the strained conformation. Chirality, and in one case, racemization of the target nickel complexes were confirmed by circular dichroism (CD) spectroscopy. Electronic structure and band assignments in experimental UV-vis and CD spectra were discussed on the basis of Density Functional Theory (DFT) and time-dependent (TD) DFT calculations.

Publication types

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

MeSH terms

Imines / chemistry
Ligands
Models, Molecular
Molecular Structure
Nickel / chemistry*
Organometallic Compounds / chemical synthesis*
Organometallic Compounds / chemistry*
Quantum Theory*

Substances

Imines
Ligands
Organometallic Compounds
Nickel