CHARGE-TRANSFER SALTS FORMED FROM REDOX-ACTIVE CUBANE CLUSTER CATIONS (M4(ETA-C5H4R)4(MU-3-E)4)N+ (M = CR, FE OR MO E = S OR SE) AND VARIOUS ANIONS

The synthesis and properties of the cluster salts [C]+[A]-{C = Mo4(eta-C5H4Pr(i))4(mu-3-S)4,* Mo4(eta-C5H4Pr(i))4(mu-3-Se)4, Fe4(eta-C5H5)4(mu-3-S)4,* Fe4(eta-C5H4Me)4(mu-3-S)4,* Cr4(eta-C5H5)4(mu-3-S)4, Cr4(eta-C5H4Me)4(mu-3-S)4, or Cr4(eta-C5H4Me)4(mu-3-Se)4; A = Fe4(NO)4(mu-3-S)4} and [Mo4(eta-C5H4Pr(i))4(mu-3-S)4]2[Os6(CO)18]* are described along with the cluster salts of tetracyanoquinodimethane (tcnq) or tetracyanoethylene (tcne) [Mo4(eta-C5H4Pr(i))4(mu-3-S)4][tcnq],* [Fe4(eta-C5H5)4(mu-3-S)4][tcnq], [Fe4(eta-C5H4Me)4(mu-3-S)4][tcnq],* [Cr4(eta-C5H5)4(mu-3-S)4][(tcnq)2], [Cr4(eta-C5H4Me)4(mu-3-S)4] [tcnq], [Cr4(eta-C5H4Me)4(mu-3-S)4][(tcnq)2], [Cr4(eta-C5H4Me)4(mu-3-Se)4][tcnq], [Cr4(eta-C5H4Me)4(mu-3-Se)4][(tcnq)2], [Mo4(eta-C5H4Pr(i))4(mu-3-Se)4][tcnq], [Mo4(eta-C5H4Pr(i))4(mu-3-Se)4][tcnq]3, and [Cr4(eta-C5H4Me)4(mu-3-S)4][tcne]. The cluster dithiolene salts [C]n+[Mo{S2C2(CF3)2}3]n- {C = Mo4(eta-C5H4Pr(i))4(mu-3-Se)4, Mo4(eta-C5H4Pr(i))4(mu-3-S)4, [Mo4(eta-C5H4Pr(i))4(mu-3-S)4]2, Cr4(eta-C5H4Me)4(mu-3-S)4, or Cr4(eta-C5H4Me)4(mu-3-Se)4} and [Mo4(eta-C5H4Pr(i))4(mu-3-S)4][Ni{S2C2(CN)2}2] are also reported. Crystal structures have been determined for the compounds marked * and also for the neutral selenium cubane [Mo4(eta-C5H4Pr(i))4(mu-3-Se)4]. The crystal structures of the cluster salts are not always those predicted from idealized ionic model considerations. Electrical conductivities and magnetic properties are described. The compound [Mo4(eta-C5H4Pr(i))4(mu-3-S)4][tcnq] has an unusual ribbon arrangement of the tcnq- anions and shows weak antiferromagnetic behaviour with T(n) almost-equal-to 12 K.