Synthesis and characterization of tetrahedral and square planar Bis(iminopyrrolyl) complexes of cobalt(II)

S A Carabineiro, L C Silva, P T Gomes, L C J Pereira, L F Veiros, Sofia I Pascu, M T Duarte, S Namorado, R T Henriques

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Abstract

A series of 2-iminopyrrole ligand precursors with increasing bulkiness [HNC4H3C(R)=N-2,6-R'2C6H3] (R = R' = H, 1 a; R = Me, R'= H, 1 b; R = H, R' = Me, 1 c; R = R' = Me, 1 d; R = H, R' = Pr-i, 1 e; R = Me, R' = iPr, 1f) were synthesized and deprotonated with NaH to give the corresponding iminopyrrolyl sodium salts 2a-f. A set of homoleptic bis-ligand Co(II) complexes of the type [CO(k(2) N,/V-NC4H3C(R)=N-2,6-R'2C6H3)21 (R = R'= H, 3a; R = Me, R'= H, 3b; R = H, R' = Me, 3c; R = R' = Me, 3d; R = H, R' = Pr-i, 3e; R = Me, R' = Pr, 3f) was prepared by reaction Of COC12 with the corresponding iminopyrrolyl sodium salts 2a-f. The new complexes were characterized by elemental analysis, magnetic susceptibility measurements, in powder and in solution, UV/vis/NIR, and, in some cases, X-ray crystallography. According to X-ray diffraction and magnetic measurements, the Co complexes 3a-e proved to be tetrahedral, which is the preferred geometry for Co(II) compounds. However, a square planar geometry is observed in the case of 3f, as determined by several characterization techniques. In this case, DFT calculations suggest the square planar geometry is slightly more stable than the tetrahedral one probably due to a combination of steric and electronic reasons.
Original languageEnglish
Pages (from-to)6880-6890
Number of pages11
JournalInorganic Chemistry
Volume46
Issue number17
DOIs
Publication statusPublished - 2007

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