EXTRACTION AND ISOLATION OF THE ONE-ELECTRON OXIDIZED [(ZR6BE)CL-18](5-) AND [(ZR6BE)CL-18](4-) CLUSTERS FROM SOLID-STATE PRECURSORS

One-electron oxidized zirconium chloride clusters were obtained from s olid state precursors Rb5Zr6Cl18B and K3Zr6Cl15Be by dissolution in CH 3CN in the presence of Et(4)NCl and isolated as the salts (Et(4)N)(4)Z r6Cl18B . 2CH(3)CN and (Et(4)N)(5)Zr6C18Be . 3CH(3)CN. (Et(4)N)(4)Zr6C l18B . 2CH(3)CN crystallizes in the space group <P(1)over bar> (#2) wi th a = 12.329(5) Angstrom, b = 12.657(6) Angstrom, c = 13.136(8) Angst rom, alpha = 118.28(4)degrees, beta = 93.45(4)degrees, gamma = 105.54( 3)degrees, V = 1696(2) Angstrom(3), and Z = 1. (Et(4)N)(5)Zr6Cl18Be . 3CH(3)CN was refined in the space group C2/c (#15) with a = 24.166(11) Angstrom, b = 13.265(6) Angstrom, c = 25.86(2) Angstrom, beta = 104.2 1(4)degrees, V = 8037(7) Angstrom(3), and Z = 4; the space group refle cts the pseudo-symmetry of the crystal, the true symmetry of the struc ture is lower. The removal of one electron from the Zr-Zr bonding HOMO of both clusters results in cluster expansion of similar magnitude in both compounds. Moisture from the added Et(4)NCl is the likely oxidan t, but the possibility that acetonitrile may be reduced by [(Zr6Be)Cl- 18](6-) is not ruled out.