Recent studies of the mixed ligand complexes (C5Me5)(C5Me4H)2Ln and (C5Me5)2(C5Me4H)Ln (Ln=Y, Lu) suggest that (C5Me4H)- ligands in the proper coordination environment can reduce dinitrogen.  Hence, (C5Me5)(C5Me4H)2Lu and (C5Me5)2(C5Me4H)Y react with N2 to form [(C5Me5)(C5Me4H)Lu]2(N2) and [(C5Me5)2Y]2(N2) with (C5Me4H)2 as the byproduct in each case.  Similar reactivity has been observed for (C5Me4H)3Sc which forms [(C5Me4H)2Sc]2(N2) and (C5Me4H)2.  All of the reactive tris(cyclopentadienyl) species have either ?1-C5Me4H or ?3-C5Me4H binding to the rare earth metal.  In contrast,  (C5Me5)(C5Me4H)2Y and (C5Me5)2(C5Me4H)Lu, which also have ?3-C5Me4H ligands do not react with N2.  This unusual (C5Me4H)- reduction reactivity has been investigated by exploring reactivity with a variety of other substrates as well as by density functional theory.  New reactions of these complexes will be described as well as DFT studies that show that the HOMOs of these compounds have electron density primarily on the ?3-C5Me4H ligand.

Dinitrogen reductive chemistry of the (C5Me4H)- ligand in tris(cyclopentadienyl) rare earth complexes

243rd National Meeting (2012)

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