Structure and properties of an oxalato-bridged dinickel(II) complex with a tetraazamacrocycle bearing an aminomethyl pendant arm, 5-aminomethyl-5R(S),12R(S)-dimethyl-1,4,8,11-tetraazacyclotetradecane
The oxalato-bridged dinickel(II) complex with the title ligand, [Ni2(LaH)2(-ox)](ClO4)2·2H2O (1), was prepared and its structure was determined by X-ray crystallography, as well as that of the monomeric nickel(II) complex, [Ni(LaH)ox]ClO4·3H2O (2). In Complexes 1 and 2, the ligand, La, is folded along the N(4)-Ni(1)-N(11) axis. The antiferromagnetic coupling between the two nickel(II) centers in 1 was revealed and the coupling constant, J = −17.4 cm−1, and g = 2.11 were estimated. It was found that the oxalato-bridged dimer 1 was readily converted to the mononuclear cis-nickel(II) complex [NiLa(OH2)](ClO4)2 (3a), in basic aqueous solution. In [NiLa(CH3CN)]I2 (3b), which was derived from 3a, the aminomethyl pendant arm is coordinated to the Ni(II) ion and La is folded along the N(1)-Ni(1)-N(8) axis.
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