The Original CoII Heteroscorpionates Revisited: On the EPR of Pseudotetrahedral CoII
作者： Robert R. Baum , William K. Myers , Samuel M. Greer , Robert M. Breece , David L. Tierney
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摘要: An examination of the solution spectroscopy a series tetrahedral bis-bispyrazolylborate complexes CoII is presented. This includes re-examination UV/Vis-NIR three stable derivatives, Bp2Co, Bp3,5Me2Co and (Ph2Bp)2Co, which showed two transitions previously unobserved, one arising from splitting near-infrared d-d transition ligand-based or charge-transfer mechanism; reevaluation Δ B led to values more in line with similar complexes. Frozen EPR suggests all are under influence non-negligible, negative zero-field splitting. contrast previous powder measurements, we show observed only subset available transitions, leading mis-assignment parent complex's electronic structure. We present proposal, based on this closely related set complexes, that 59Co hyperfine coupling sometimes pseudotetrahedral at X-band fact indicative an MS = ± 3/2 ground level (D < 0), originating nominally forbidden ΔMS 3 along g∥.
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