Synthesis of Zr-Re-containing polyhydrides by amine elimination

Article abstract of DOI:10.1016/0304-5102(89)80169-5

The reaction between Zr(C₅H₅)₂(X)(NMe₂) and ReH₇(PPh₃)₂ results in the production of the heterometallic polyhydrides (C₅H₅)₂Zr(X)[H₆Re (PPh₃)₂] [(I), X = Cl; (II), X = NMe₂] with the elimination of HNMe₂. Both compounds were characterized spectroscopically and the structure of (I) was determined by X-ray diffraction. Full-matrix least squares refinement converged at R = 6.55% and R_w = 6.14%. ReH₇(PPh₃)₂ also reacts with Zr(NMe₂)₄ in a 1:1 or 2:1 mole ratio to produce (NMe₂)₃Zr[H₆Re(PPh₃)₂] (III) and (NMe₂)₂Zr [H₆Re(PPh₃)₂]₂ (IV) with the elimination of one or two equivalents of HNMe₂, respectively. The structure pf (IV) was determined by X-ray diffraction. Full-matrix least-squares refinement converged at R = 10.4% and R_w = 9.3%. The reactivity of these compounds with simple substrates such as CO and CO₂ has been surveyed and compared with that of the previously known Zr-Re polyhydride (C₅H₅)₂Zr(H)[H₆Re(PMePh₂)₂].