Molecular Structures of Carbonyl-Linked Bis(dioxolene) Complexes: Can a Carbonyl Group Act as an Effective Ferromagnetic Coupler?

Molecular structures of two bis(ZnIIdioxolene) complexes are described:  (TpCum,MeZn)21-H2 (C106H123.50B2N12O10Zn2), tetragonal, P4/ncc, a = 25.1810(2) Å, b = 25.1810(2) Å, c = 34.7744(2) Å, α = 90°, β = 90°, γ = 90°,
Z = 8; (TpCum,MeZn)21-H (C101H120B2N12O6Zn2), triclinic, P1̄, a = 13.6624(2) Å, b = 13.80920(10) Å, c =
26.62340(10) Å, α = 96.6910(10)°, β = 91.8560(10)°, γ = 109.0190(10)°, Z = 2. One of the complexes,
(TpCum,MeZn)21-H2, has two protonated catecholate ligands, while the other complex, (TpCum,MeZn)21-H, has
one protonated catecholate and one semiquinone ligand. When reacted with PbO2, a labile S = 1, bis(ZnIIsemiquinone) complex is formed in which the two semiquinones are attached to a common carbonyl group.

本数据集描述了两种双（二氧杂环戊烯合锌(II)）(bis(ZnIIdioxolene))配合物的分子结构：(TpCum,MeZn)₂1-H₂（化学式C₁₀₆H₁₂₃.₅₀B₂N₁₂O₁₀Zn₂），属四方晶系，空间群为P4/ncc，晶胞参数为a=25.1810(2) Å，b=25.1810(2) Å，c=34.7744(2) Å，α=90°，β=90°，γ=90°，Z=8；(TpCum,MeZn)₂1-H（化学式C₁₀₁H₁₂₀B₂N₁₂O₆Zn₂），属三斜晶系，空间群为P1̄，晶胞参数为a=13.6624(2) Å，b=13.80920(10) Å，c=26.62340(10) Å，α=96.6910(10)°，β=91.8560(10)°，γ=109.0190(10)°，Z=2。其中一种配合物(TpCum,MeZn)₂1-H₂含有两个质子化儿茶酚酸酯配体，而另一种配合物(TpCum,MeZn)₂1-H则含有一个质子化儿茶酚配体与一个半醌配体。当与二氧化铅（PbO₂）反应时，可生成一种自旋多重度为S=1的不稳定双（半醌合锌(II)）配合物，该配合物的两个半醌基团连接于同一个羰基之上。