Abstract
The trioxo complex (η 5-C 5Me 5)ReO 3 ( 1) undergoes partial deoxygenation in the presence of the Lewis base triphenylphosphane. When this reaction is conducted in tetrahydrofuran solution with rigorous exclusion of air, the dinuclear, very oxygen-sensitive d 2-Re V derivative 2 of composition (η 5-C 5Me 5) 2Re 2O 4 is cleanly formed. In the presence of trace amounts of oxygen, however, a second reaction pathway is opened up, which leads to the tetranuclear Re V/Re VII complex 3 in 30–60% yield. This compound is structurally derived from the dinuclear species 2, in that one of the two terminal oxo groups is replaced by two O-coordinated perrhenate ligands; in keeping with the requirements of the EAN rule and supported by the bond length of 265.1(1) pm, the doubly oxygen-bridged Re V-Re V interaction is best interpreted in terms of a metal—metal double bond (single-crystal X-ray diffraction study). Finally, upon treatment of 1 with triphenylphosphane in air-saturated solutions of tetrahydrofuran, the ionic cluster compound 4 of net composition (C 5Me 5) 3Re 5O 14 is surprisingly formed in 70–90% yield. This latter complex exhibits the C 3-symmetrical cation [(η 5-C 5Me 5) 3Re 3(μ-O) 6] 2+, with the two counter-ions being isolated perrhenate groups. The metal—metal distances within the cyclic cation are crystallographically identical and amount to 274.7(2) pm (single-crystal X-ray diffraction study).
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