Coordination and reductive chemistry of tetraphenylborate complexes of trivalent rare earth metallocene cations, [(C5Me5)2Ln][(μ-Ph)2BPh2].
Coordination and reductive chemistry of tetraphenylborate complexes of trivalent rare earth metallocene cations, [(C5Me5)2Ln][(μ-Ph)2BPh2].
复制标题
三价稀土茂金属阳离子四苯硼酸盐配合物[(C5Me5)2Ln][(μ-Ph)2BPh2]的配位和还原化学。
作者：
Matthew R. MacDonald;J. Ziller;W. Evans
研究了稀土金属茂阳离子[（C（5）Me（5））（2）Ln][（μ-Ph）（2）BPh（2）]（Ln = Y，1; Sm，2）的四苯硼酸盐与底物的反应性。用NaN（3），1-金刚烷基叠氮化物，丙酮，二苯甲酮，菲咯啉，吡啶，偶氮苯，和吩嗪的结果进行了描述。不仅分离出了配位复合物，还观察到了（Bph（4））（-）对底物的还原。配合物1与NaN（3）反应形成叠氮化物[（C（5）Me（5））（2）YN（3）]（x），3，当从1和1-金刚烷基叠氮化物获得时，其结晶为[（C（5）Me（5））（2）Y（μ-N（3））]（3），4。钐类似物[（C（5）Me（5））（2）SmN（3）]（x），5可以类似地从2和NaN（3）产生，并从MeCN中结晶为[（C（5）Me（5））（2）Sm（NCMe）（μ-N（3））]（3），6和{[（C（5）Me（5））（2）Sm（μ-N（3））][（C（5）Me（5））（2）Sm（NCMe）（μ-N（3））]}（n），7。配合物1和2分别与化学计量的丙酮和二苯甲酮反应生成酮加合物[（C（5）Me（5））（2）Ln（OCMe（2））（2）][BPh（4）]（Ln = Y，8; Sm，9）和[（C（5）Me（5））（2）Ln（OCPh（2））（2）][BPh（4）]（Ln = Y，10; Sm，11）。邻菲咯啉（phen）与1配位形成[（C（5）Me（5））（2）Y（phen）][BPh（4）]，12。配合物1和2与吡啶（py）反应生成[（C（5）Me（5））（2）Ln（py）（2）][BPh（4）]，（Ln = Y，13; Sm，14）。络合物3、8、10和12也可以由溶剂化阳离子[（C（5）Me（5））（2）Y（THF）（2）][BPh（4）]制备。1与PhNNPh反应生成抗磁性加合物[（C（5）Me（5））（2）Y（PhNNPh）][BPh（4）]，15，其在苯中通过（BPh（4））（-）的单电子还原转化为自由基阴离子络合物（C（5）Me（5））（2）Y（PhNNPh），16。络合物1类似地与吩嗪（phz）反应以产生第一稀土吩嗪自由基阴离子络合物{[（C（5）Me（5））（2）Y]（2）（phz）}{BPh（4）}，17。吩嗪在17中被（BPh（4））（-）进一步还原，得到[（C（5）Me（5））（2）Y]（2）（phz），18，其含有常见的（phz）（2-）二价阴离子。本文还报道了（BPh（4））（-）对芴酮的还原反应。
The reactivity of the tetraphenylborate salts of the rare earth metallocene cations [(C(5)Me(5))(2)Ln][(μ-Ph)(2)BPh(2)] (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 NaN(3), 1-adamantyl azide, acetone, benzophenone, phenanthroline, pyridine, azobenzene, and phenazine are described. Not only were coordination complexes isolated, but substrate reduction by (BPh(4))(-) was also observed. Complex 1 reacts with NaN(3) to form the azide [(C(5)Me(5))(2)YN(3)](x), 3, which crystallizes as [(C(5)Me(5))(2)Y(μ-N(3))](3), 4, when obtained from 1 and 1-adamantyl azide. The samarium analogue [(C(5)Me(5))(2)SmN(3)](x), 5, can be produced similarly from 2 and NaN(3) and crystallized from MeCN as [(C(5)Me(5))(2)Sm(NCMe)(μ-N(3))](3), 6, and {[(C(5)Me(5))(2)Sm(μ-N(3))][(C(5)Me(5))(2)Sm(NCMe)(μ-N(3))]}(n), 7. Complexes 1 and 2 react with stoichiometric amounts of acetone and benzophenone to form the ketone adducts [(C(5)Me(5))(2)Ln(OCMe(2))(2)][BPh(4)] (Ln = Y, 8; Sm, 9) and [(C(5)Me(5))(2)Ln(OCPh(2))(2)][BPh(4)] (Ln = Y, 10; Sm, 11), respectively. Phenanthroline (phen) coordinates to 1 to form [(C(5)Me(5))(2)Y(phen)][BPh(4)], 12. Complexes 1 and 2 react with pyridine (py) to form [(C(5)Me(5))(2)Ln(py)(2)][BPh(4)], (Ln = Y, 13; Sm, 14). Complexes 3, 8, 10, and 12 can also be made from the solvated cation [(C(5)Me(5))(2)Y(THF)(2)][BPh(4)]. The reaction of 1 with PhNNPh yields the diamagnetic adduct [(C(5)Me(5))(2)Y(PhNNPh)][BPh(4)], 15, which transforms in benzene to the radical anion complex (C(5)Me(5))(2)Y(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(5)Me(5))(2)Y](2)(phz)}{BPh(4)}, 17. Further reduction of phenazine by (BPh(4))(-) in 17 yields [(C(5)Me(5))(2)Y](2)(phz), 18, which contains the common (phz)(2-) dianion. The reduction of fluorenone by (BPh(4))(-) is also reported.