| Abstract
| - Fluoroalkoxide size and nucleophilicity(O(CF3)Me2 →O(CF3)2Me) influence the stoichiometry ofthe heterometallic species formed: (Me3NO)2Ba2Cu4[O(CF3)Me2]8vs(THF)2Ba2Cu2[O(CF3)2Me]6(illustrated here).
- Reaction of HORF and in situ synthesized[Ba(ORF)2] (fromBa[N(SiMe3)2]2(THF)2and HORF) with CuMesyields, in THF,[(THF)2Ba2Cu2(OCMe(CF3)2)6].In the case of HORF =HOCMe2CF3, only upon additionofMe3NO is a soluble product obtained: [(Me3NO)2Ba2Cu4(OCMe2CF3)8].[(THF)2Ba2Cu2(OCMe(CF3)2)6]has asquare-planar Ba2Cu2O4 corestructure with two additional alkoxides bridging the two bariums,giving the bariuma tbp coordination environment. The structure of[(Me3NO)2Ba2Cu4(OCMe2CF3)8]is markedly different in thatit has one more Cu−(OR) unit inserted into the Ba−(OR)−Ba unit.This gives the Ba2Cu4 core structuretheshape of an octahedron and barium a square-pyramidal coordinationenvironment. These structures are comparedand contrasted with the structures of[Ba2Cu4(OCEt3)8],[(Et3PO)2Ba2Cu4(OtBu)8],and[(Me3NO)2Ba2Cu4(OtBu)8].
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