Synthesis and Coordination Chemistry of 2-(Di-2-pyridylamino)pyrimidine: Structural Aspects of Spin Crossover in an FeII Complex

Rachel Crees, Boujemma Moubaraki, Keith Murray, Christopher Sumby

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2 Citations (Scopus)

Abstract

2-(Di-2-pyridylamino)pyrimidine (L), a potentially ditopic tetradentate ligand, was synthesized from commercially available di-2-pyridylamine and 2-chloropyrimidine. Despite being capable of bridging two metal atoms with bidentate chelation of both metal centres, L prefers to chelate or bridge through the more basic pyridyl donors of the di-2-pyridylamine moiety. Mononuclear trans-[Fe(NCS) 2(L) 2] and [Cu(L) 2(H 2O)](BF 4) 2·H 2O complexes, and a discrete [Ag 2(L) 4](PF 6) 2 metallo-macrocycle, were isolated and structurally characterized by X-ray crystallography. A mononuclear palladium complex [PdCl 2(L)]·(solvate), where solvate=1/ 2H 2O or CH 2Cl 2, was also readily obtained in 71% yield. One example of the ligand acting as a bis(bidentate) bridging ligand was observed in a dinuclear [(PdCl 2) 2(L)]·3/4H 2O complex that was obtained only in very low yield (∼3%) from the reaction that produced [PdCl 2(L)]·1/2H 2O. trans-[Fe(NCS) 2(L) 2] undergoes a temperature-dependent high-spinlow-spin crossover at ∼205K that was observed by X-ray crystallography and magnetic measurements, and attempts were made to understand the structural basis of this process. Despite efforts to isolate examples of L bridging two iron(ii) centres, only the mononuclear trans-[Fe(NCS) 2(L) 2] species could be obtained.

Original languageEnglish
Pages (from-to)842-850
Number of pages9
JournalAustralian Journal of Chemistry
Volume65
Issue number7
DOIs
Publication statusPublished - 2012

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