Synthesis and Coordination Chemistry of 2-(Di-2-pyridylamino)pyrimidine; Structural Aspects of Spin Crossover in an FeII Complex*
Rachel S. Crees A , Boujemma Moubaraki B , Keith S. Murray B and Christopher J. Sumby A C
+ Author Affiliations
- Author Affiliations
A School of Chemistry and Physics, University of Adelaide, Adelaide, SA 5005, Australia.
B School of Chemistry, Monash University, Clayton, Vic. 3800, Australia.
C Corresponding author. Email: christopher.sumby@adelaide.edu.au
Australian Journal of Chemistry 65(7) 842-850 https://doi.org/10.1071/CH12045
Submitted: 25 January 2012 Accepted: 26 February 2012 Published: 18 May 2012
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(H2O)](BF4)2·H2O complexes, and a discrete [Ag2(L)4](PF6)2 metallo-macrocycle, were isolated and structurally characterized by X-ray crystallography. A mononuclear palladium complex [PdCl2(L)]·(solvate), where solvate = 1/2H2O or CH2Cl2, was also readily obtained in 71 % yield. One example of the ligand acting as a bis(bidentate) bridging ligand was observed in a dinuclear [(PdCl2)2(L)]·3/4H2O complex that was obtained only in very low yield (~3 %) from the reaction that produced [PdCl2(L)]·1/2H2O. trans-[Fe(NCS)2(L)2] undergoes a temperature-dependent high-spin–low-spin crossover at ~205 K 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.
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