Macrocyclic Nickel(II) Complexes Coligated by Hydrosulfide and Hexasulfide Ions : Syntheses, Structures, and Magnetic Properties of [NiII2L(μ-SH)]+ and [{LNiII2}2(μ-S6)]2+

摘要: The borohydride complex [Ni(II)2L(mu-BH4)]+ (3) where L(2-) represents a sterically demanding hexaaza-dithiophenolate ligand reacts rapidly with elemental sulfur in acetonitrile at ambient temperature to produce the cationic complexes [Ni(II)2L(mu-SH)]+ (4) and [(Ni(II)2L) 2(mu-S6)]2+ (6). Both were isolated as ClO4(-) or BPh4(-) salts characterized by IR UV/vis spectroscopy X-ray crystallography. Complex 4 (also accessible from [Ni(II)2L(ClO4)]+ (5) Na2S.9H2O) features an unprecedented N3Ni(II)(mu-SR)2(mu-SH)Ni(II)N3 core structure, hydrosulfide being deeply buried binding-cavity of bowl-shaped [Ni(II)2L]2+ complex. In 6, helical S6(2-) chain, structure reminiscent that plastic sulfur, is almost completely encapsulated two subunits. contrast other triply sulfur-bridged N3Ni(II)(SR)3Ni(II)N3 structures whose ground states are typically S = 0, reveals 2 ground-state which attained ferromagnetic exchange interaction between Ni(II) (S 1) ions ( J 18 cm (-1), H -2JS1S2). Intradimer interactions also present 6 23 (-1)). A qualitative explanation for this difference offered.