1287739-20-1Relevant articles and documents
Coordination and Reductive Chemistry of Tetraphenylborate Complexes of Trivalent Rare Earth Metallocene Cations, [(C5Me5) 2Ln][(μ-Ph)2BPh2]
Macdonald, Matthew R.,Ziller, Joseph W.,Evans, William J.
, p. 4092 - 4106 (2011)
The reactivity of the tetraphenylborate salts of the rare earth metallocene cations [(C5Me5)2Ln][(μ-Ph) 2BPh2] (Ln = Y, 1; Sm, 2) has been investigated with substrates that undergo reduction with f element complexes to probe metal-substrate interactions prior to reduction. Results with NaN3, 1-adamantyl azide, acetone, benzophenone, phenanthroline, pyridine, azobenzene, and phenazine are described. Not only were coordination complexes isolated, but substrate reduction by (BPh4)- was also observed. Complex 1 reacts with NaN3 to form the azide [(C5Me 5)2YN3]x, 3, which crystallizes as [(C5Me5)2Y(μ-N3)]3, 4, when obtained from 1 and 1-adamantyl azide. The samarium analogue [(C 5Me5)2SmN3]x, 5, can be produced similarly from 2 and NaN3 and crystallized from MeCN as [(C5Me5)2Sm(NCMe)(μ-N3)] 3, 6, and {[(C5Me5)2Sm(μ-N 3)][(C5Me5)2Sm(NCMe)(μ-N 3)]}n, 7. Complexes 1 and 2 react with stoichiometric amounts of acetone and benzophenone to form the ketone adducts [(C 5Me5)2Ln(OCMe2)2] [BPh4] (Ln = Y, 8; Sm, 9) and [(C5Me5) 2Ln(OCPh2)2][BPh4] (Ln = Y, 10; Sm, 11), respectively. Phenanthroline (phen) coordinates to 1 to form [(C 5Me5)2Y(phen)][BPh4], 12. Complexes 1 and 2 react with pyridine (py) to form [(C5Me5) 2Ln(py)2][BPh4], (Ln = Y, 13; Sm, 14). Complexes 3, 8, 10, and 12 can also be made from the solvated cation [(C 5Me5)2Y(THF)2][BPh4]. The reaction of 1 with PhNNPh yields the diamagnetic adduct [(C5Me 5)2Y(PhNNPh)][BPh4], 15, which transforms in benzene to the radical anion complex (C5Me5) 2Y(PhNNPh), 16, via a one electron reduction by (BPh 4)-. Complex 1 similarly reacts with phenazine (phz) to produce the first rare earth phenazine radical anion complex {[(C 5Me5)2Y]2(phz)}{BPh4}, 17. Further reduction of phenazine by (BPh4)- in 17 yields [(C5Me5)2Y]2(phz), 18, which contains the common (phz)2- dianion. The reduction of fluorenone by (BPh4)- is also reported.
