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Science 18 September 1964:
Vol. 145. no. 3638, pp. 1305 - 1307
DOI: 10.1126/science.145.3638.1305
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Articles

Mononuclear and Polynuclear Chemistry of Rhenium (III): Its Pronounced Homophilicity

F. A. Cotton 1, N. F. Curtis 1, C. B. Harris 1, B. F. G. Johnson 1, S. J. Lippard 1, J. T. Mague 1, W. R. Robinson 1, and J. S. Wood 1

1 Department of Chemistry, Massachusetts Institute of Technology, Cambridge

Extensive chemical, spectrophotometric, and x-ray structural studies have shown that trivalent rhenium is strongly homophilic—that is, it tends to form bonds to other Re111 atoms—and it forms at least three different series of [ReX4]nn- complexes. The mononuclear, square complex, [ReBr4]-, adds two water molecules to give trans-[ReBr4(H2O)2]-. The binuclear complexes [Re2Cl8]2- and [Re2Br8]2- have strong Re-Re bonds, unsupported by halide bridges. The trinuclear species, [Re3X12]3- or Re3X9L3, contain the triangular Re3X9 clusters. Use of ReCI3 appears always to lead directly to products containing Re3Cl9; this unit exists in ReCl3 itself and does not appear to be kinetically labile. The [Re2X8]2- ions are obtained by reduction of ReO4- in aqueous HCl or HBr. Salts of [ReBr4(H2O)2]- can be obtained directly from solutions of ReBr3 in HBr along with numerous other compounds, some containing trinuclear clusters.


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