Dinitrogen Reduction, Sulfur Reduction, and Isoprene Polymerization via Photochemical Activation of Trivalent Bis(cyclopentadienyl) Rare-Earth-Metal Allyl Complexes

作者：Fieser Megan E; Johnson Casey W; Bates Jefferson E; Ziller Joseph W; Furche Filipp^*; Evans William J

来源：Organometallics, 2015, 34(17): 4387-4393.

DOI：10.1021/acs.organomet.5b00613

Dinitrogen can be reduced by photochemical activation of the trivalent rare-earth-metal bis(pentamethylcyclopentadienyl) allyl complexes (C3Me5)(2)Ln(eta(3)-C3H4R) (Ln = Y, Lu; R = H, Me) to form the (N=N)(2-)complexes [(C5Me5)(2)Ln](2)(mu-eta(2):eta(2)-N-2). This demonstrates that productive organolanthanide photochemistry is not limited to complexes of the unusual (eta(3)-C5Me4H)(-) ligand in the heteroleptic complexes (C5Me5)(2)(C5Me4H)Ln and (C5Me5)-(C5Me4H)(2)Ln. Photolytic activation of (C5Me5)(2)Ln(eta(3)-C3H5) (Ln = Y, Lu) in the presence of isoprene provides a rare photopolymerization route to polyisoprene. Sulfur can also be reduced by photolysis of (C5Me5)(2)Ln(eta(3)-C3H5) (Ln = Y, Lu) to generate the (S)(2-) complexes, [(C5Me5)(2)Ln](2)(mu-S), which have variable Ln-S-Ln angles depending on crystallization conditions.

• 出版日期2015-9-14