(Ni2), (Ni3) and (Ni2 + Ni3): a unique example of isolated and cocrystallized Ni2 and Ni3 complexes

Mukherjee, Pampa ; Drew, Michael G. B. ; Gomez-García, Carlos J. ; Ghosh, Ashutosh (2009) (Ni2), (Ni3) and (Ni2 + Ni3): a unique example of isolated and cocrystallized Ni2 and Ni3 complexes Inorganic Chemistry, 48 (11). pp. 4817-4827. ISSN 0020-1669

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic802385c

Related URL: http://dx.doi.org/10.1021/ic802385c


Structural and magnetic characterization of compound {[Ni2(L 2(OAc) 2][Ni3(L) 2(OAc)4]}•2CH3CN (3) (HL = the tridentate Schiff base ligand, 2-[(3-methylamino-propylimino)-methyl]-phenol) shows that it is a rare example of a crystal incorporating a dinuclear Ni(II) compound, [Ni 2(L) 2(OAc) 2] and a trinuclear one, [Ni3(L) 2(OAc)4]. Even more unusual is the fact that both Ni(II) complexes, [Ni 2(L) 2(OAc) 2] (1) and [Ni3(L) 2(OAc)4(H 2O) 2]•CH 2Cl 2•2CH3OH (2), have also been isolated and structurally and magnetically characterized. The structural analysis reveals that the dimeric complexes [Ni 2(L) 2(OAc) 2] in cocrystal 3 and in compound 1 are almost identical-in both complexes, the Ni (II) ions possess a distorted octahedral geometry formed by the chelating tridentate ligand (L), a chelating acetate ion, and a bridging phenoxo group with very similar bond angles and distances. On the other hand, compound 2 and the trinuclear complex in the cocrystal 3 show a similar linear centrosymmetric structure with the tridentate ligand coordinated to the terminal Ni (II) and linked to the central Ni (II) by phenoxo and carboxylate bridges. The only difference is that a water molecule found in 2 is not present in the trinuclear unit of complex 3; instead, the coordination sphere is completed by an additional bridging oxygen atom from an acetate ligand. Variable-temperature (2−300 K) magnetic susceptibility measurements show that the dinuclear unit is antiferromagnetically coupled in both compounds (2J = −36.18 and −29.5 cm−1 in 1 and 3, respectively), whereas the trinuclear unit shows a very weak ferromagnetic coupling in compound 3 (2J = 0.23 cm−1) and a weak antiferromagnetic coupling in 2 (2J = −8.7(2) cm−1) due to the minor changes in the coordination sphere.

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