NDLI: Synthesis and first use of pyridine-2,6-diylbis(pyrazine-2-ylmethanone) in metal cluster chemistry: a $\{Mn^{III}_{3}Na_{2}\}$ complex with an ideal trigonal bipyramidal geometry

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Metallinos, Costa Teat, Simon J. Escuer, Albert Wilson-konderka, Cody Giannopoulos, Dimosthenis P. Gagnon, Kevin J. Stamatatos, Theocharis C.
Description	Author Affiliation: Giannopoulos DP ( Department of Chemistry, Brock University, St. Catharines, Ontario, L2S3A1, Canada. tstamatatos@brocku.ca.)
Abstract	The successful organic synthesis of a new dipyrazole/pyridine-dicarbonyl organic molecule, namely pyridine-2,6-diylbis(pyrazine-2-ylmethanone) [(pz)CO(py)CO(pz)], followed by its employment in Mn coordination chemistry has yielded the neutral cluster compound $[Mn_{3}Na_{2}O(N_{3})_{3}(L)_{3}]$ (1), where $L^{2−}$ is the $(pz)C(CH_{2}COCH_{3})(O^{−})(py)C(CH_{2}COCH_{3})(O^{−})(pz)$ dianion. The latter group was formed in situ, presumably by the nucleophilic attack of the carbanion $^{−}CH_{2}COCH_{3}$ to the carbonyl carbon atoms of (pz)CO(py)CO(pz), in the presence of $Mn^{n+}$ ions under basic conditions and in solvent $Me_{2}CO.$ Complex 1 possesses an almost ideal trigonal bipyramidal topology, with the two $Na^{I}$ ions occupying the apical positions and the three $Mn^{III}$ ions residing in the equatorial trigonal plane. The bridging ligation about the metal ions is provided by a $μ_{3}-O^{2−}$ ion and six $μ-OR^{−}$ groups from the $L^{2−}$ ligand, while peripheral ligation is completed by three terminal azido groups and the pyridine N and carbonyl O atoms of $L^{2−}.$ Magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the paramagnetic $Mn^{III}$ centres; the use of an anisotropic, equilateral $Mn^{III}_{3}$ triangle model allowed us to fit the magnetic data and obtain the best-fit parameters: J = −10.8 $cm^{−1},$ D = −5.3 $cm^{−1},$ and g = 1.99. The combined results demonstrate the rich chemical reactivity of carbonyl groups and the ability of poly-ketone ligands to stabilize cluster compounds with unprecedented structural motifs and interesting architectures.
ISSN	14779226
Issue Number	9
Journal	Dalton Trans.
Volume Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-03-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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