B. Borup et al., HETEROMETALLIC FLUOROALKOXIDES OF BARIUM AND COPPER(I) - SYNTHESES AND STRUCTURES OF [(ME3NO)(2)BA2CU4(TFTB)(8)] AND [(THF)(2)BA2CU2(HFTB)(6)], Inorganic chemistry, 36(22), 1997, pp. 5058-5063
Reaction of HORF and in situ synthesized [Ba(ORF)(2)] (from Ba[N(SiMe3
)(2)](2)(THF)(2) and HORF) with CuMes yields, in THF, [(THF)(2)Ba2Cu2(
OCMe(CF3)(2))(6)]. In the case of HORF = HOCMe2CF3, only upon addition
of Me3NO is a soluble product obtained: [(Me3NO)(2)Ba2Cu4(OCMe2CF3)(8
)]. [(THF)(2)Ba2Cu2(OCMe(CF3)(2))(6)] has a square-planar Ba2Cu2O4 cor
e structure with two additional alkoxides bridging the two bariums, gi
ving the barium a tbp coordination environment. The structure of [(Me3
NO)(2)Ba2Cu4(OCMe2CF3)(8)] is markedly different in that it has one mo
re Cu-(OR) unit inserted into the Ba-(OR)-Ba unit. This gives the Ba2C
u4 core structure the shape of an octahedron and barium a square-pyram
idal coordination environment. These structures are compared and contr
asted with the structures of [Ba2Cu4(OCEt3)(8)], [(Et3PO)(2)Ba2Cu4((OB
u)-Bu-t)(8)], and [(Me3NO)(2)Ba2Cu4((OBu)-Bu-t)8].