Solvent-Dependent Access to Two Different Ni4II Core Topologies from the First Use of Pyridine-2,6-dimethanol in Nickel(ii) Cluster Chemistry

Abstract

The use of pyridine-2,6-dimethanol, pdmH2, in reactions with nickel(ii) acetate has led to two Ni4 clusters, depending on the solvent. [Ni4(O2CMe)4(pdmH)4]·MeCN (1·MeCN) can be obtained from MeCN and [Ni4(O2CMe)6(pdmH)2(EtOH)2]·1.2EtOH (2·1.2EtOH) from EtOH. Each cluster can be converted into the other in the appropriate solvent. The tetranuclear cluster molecule 1 possesses a distorted cubane {Ni4(μ3-OR)4}4+ core (RO– = pdmH–) with the NiII atoms and the alkoxide-type oxygen atoms from the η3 : η1 : μ3 pdmH– ligands occupying alternate vertices of the cube; four η1 : η1 : μ MeCO2– groups cap four faces of the cube. The four NiII atoms in molecule 2 are located at four vertices of a defective dicubane and are bridged by six oxygen atoms, two μ3 from the η3 : η1 : η1 : μ3 pdmH– ligands and four from four monoatomically bridging MeCO2– groups; peripheral ligation is provided by two η1 : η1 : μ MeCO2– groups and two terminal EtOH ligands. IR data are discussed in terms of the coordination modes of the ligands. Variable-temperature direct-current magnetic susceptibility data of 1 and 2 were modelled with two and three J values respectively, indicating diamagnetic ground states (S = 0). The sign and the magnitude of the J values are discussed in terms of structural features of the complexes.