P₄ Activation by Lanthanum and Lutetium Naphthalene Complexes Supported by a Ferrocene Diamide Ligand

Abstract

Two rare‐earth (La and Lu) naphthalene complexes supported by a ferrocene diamide ligand activate P4 under ambient conditions to form M3P7 species exclusively. The resulting complexes feature a Zintl‐type polyphosphide P73– unit stabilized by three lanthanide fragments. The reported metal complexes were characterized by X‐ray crystallography, multinuclear NMR spectroscopy, and elemental analysis.

Reactivity and Properties of Metal Complexes Enabled by Flexible and Redox-Active Ligands with a Ferrocene Backbone

“…40,44 Our group focused on the reduction chemistry of rare-earth metal complexes with non-innocent  ligands, followed by a small molecule activation study. 47,51 Much of the work was summarized in previous reviews. 27,28,40 Herein, we are going to highlight the role of the ferrocene ligand in stabilizing unusual moieties and promoting unprecedented reactivity.…”

Aromatic C–F Bond Activation by Rare-Earth-Metal Complexes

“…Herein, we report the C-F bond activation of C6F6 by 1-M/KC8 to give metal fluoride and metal perfluorophenyl products. Moreover, the previously reported [(NN TBS )M(THF)x]2(μ-C10H8) (4-M2, M = Sc, x = 0; M = Y or Lu, x = 1) [63][64]66 was able to activate C6F6 to give the same products.…”

“…As part of our group's continuing efforts to explore the chemistry of rare-earth metals and actinides supported by ferrocene-derived ligands, [55][56][57][58][59][60][61][62] especially redox reactions in the presence of arenes, [63][64][65][66][67][68][69][70][71] we discovered a bimetallic cleavage of the C-H bond of benzene by (NN TBS ) . In addition, the C-H bond activation of a naphthalene dianion sandwiched between two lutetium ions in the previously isolated [(NN TBS )Lu(THF)]2(μ-C10H8) (4-Lu2) was observed upon moderate heating (Scheme 2c).…”

Molecular Pnictogen Activation by Rare Earth and Actinide Complexes

“…Reaction of the scandium arene inverse-sandwich complexes [{Fe(1-NSi (84)) [125]. The valence tautomerisation of P7 3− in 83, which occurs at a similar temperature to Li3P7 but does not require donor solvents, was proposed to take place by a lanthanum-assisted mechanism involving simultaneous formation and breaking of 4 La-P bonds.…”