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Issue 34, 2016
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Unique molecular geometries of reduced 4- and 5-coordinate zinc complexes stabilised by diiminopyridine ligand

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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.

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

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Publication details

The article was received on 18 May 2016, accepted on 29 Jul 2016 and first published on 29 Jul 2016


Article type: Paper
DOI: 10.1039/C6DT02001A
Citation: Dalton Trans., 2016,45, 13440-13448
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    Unique molecular geometries of reduced 4- and 5-coordinate zinc complexes stabilised by diiminopyridine ligand

    T. Chu, L. Belding, P. K. Poddutoori, A. van der Est, T. Dudding, I. Korobkov and G. I. Nikonov, Dalton Trans., 2016, 45, 13440
    DOI: 10.1039/C6DT02001A

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