Unique molecular geometries of reduced 4- and 5-coordinate zinc complexes stabilised by diiminopyridine ligand

Terry Chu, Lee Belding, Prashanth K. Poddutoori, Art Van Der Est, Travis Dudding, Ilia Korobkov, Georgii I. Nikonov

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

Stepwise reduction of the diiminopyridine (dimpyr) complex, dimpyrZnCl2, by KC8 leads to molecular zinc compounds dimpyrZnCl (2) and dimpyrZnCl(DMAP) (3, DMAP = 4-dimethylaminopyridine), which were characterized by X-ray diffraction and EPR spectroscopy. Compound 2 shows an unusual nearly square planar geometry of the zinc atom equally ligated by two imine groups. X-ray crystallographic and EPR data suggest significant delocalization of the zinc 4p electron onto the non-innocent dimpyr ligand. The chloride in 2 can also be substituted by a methyl group upon addition of methyl lithium to generate compound 4, dimpyrZnMe. The novel alkylzinc compound displayed approximate square planar geometry around the zinc centre and significant delocalization of electron density onto the dimpyr ligand, as revealed by X-ray crystallographic studies and EPR spectroscopy, akin to 2. Further reduction of 3 leads to compound 5, dimpyrZn(DMAP)2. X-ray diffraction study of 5 revealed an unprecedented see-saw geometry around the four-coordinate zinc center with significant electron density transfer to the dimpyr ligand, supported by DFT calculations.

Original languageEnglish (US)
Pages (from-to)13440-13448
Number of pages9
JournalDalton Transactions
Volume45
Issue number34
DOIs
StatePublished - 2016

Bibliographical note

Funding Information:
G. I. N. acknowledges the financial support of the Petroleum Research Fund administered by the American Chemical Society. The Natural Sciences and Engineering Research Council of Canada is thanked for support in the form of Discovery Grants to A. v. d. E. and T. D. and for an Alexander Graham Bell Canada Graduate Scholarship to L. B. T. C. is grateful to the Government of Ontario for an Ontario Graduate Scholarship. SHARCNet is acknowledged for the computing resources provided.

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