Unprecedented Linking of Two Polyoxometalate Units with a Metal−Metal Multiple Bond

The reaction of (Bu(4)N)(2)[Re(2)Cl(8)] with lacunary Keggin polyoxometalate K(7)[PW(11)O(39)] in water produces a new dumbbell-shaped heteropolyoxometalate anion, [Re(2)(PW(11)O(39))(2)](8-), whose structure contains a central Re(2) core with a quadruple bond between Re atoms (Re-Re 2.25 A), coordinated to two polyoxometalate units. This complex represents the first example of the direct linking of two polyoxometalate units via a metal-metal multiple bond. The compounds were characterized by X-ray analysis, IR, and electrospray ionization mass spectrometry.