Insertion of ketenes into lanthanocene n-butylamide and imidazolate complexes

Evaluation of Volatility and Thermal Stability in Monomeric and Dimeric Lanthanide(III) Complexes Containing Enaminolate Ligands

“…Only a few examples of lanthanide complexes containing enolate-based ligands have been structurally characterized. A common feature of previously reported complexes is that the enolate moieties are part of more complex chelating ligands. − The CC double-bond lengths within the enolate fragments range from 1.33 to 1.37 Å. − These previously reported bond lengths are close to the values observed herein. A series of structurally characterized lanthanide­(III) aryloxides provides Ln–O bond length comparisons with some of the complexes reported herein.…”

Reactions of Cp3Y with Benzophenone: A Simple and Efficient Method for Transformation of Unsubstituted Cyclopentadienyl to Bridged ansa-Cyclopentadienyl/Alkoxyl Ligand

“…In addition, whether the resulting ring-substituted ligands could regenerate the η 5 -bonding mode remains unexplored in organometallic chemistry of main and rare earth metals, although it has proven successful for a few large sterically crowded lanthanocenes such as (C 5 Me 4 R) 3 Ln, (Flu) 2 Ln(THF) 2 (Flu = fluorenyl), and (Ind) 2 Yb(THF) 2 (Ind = indenyl) and a variety of metallocene complexes of main metals to undergo insertions with unsaturated substrates. During our research into the reactivity of organolanthanides toward ketenes, we observed in one case that Cp 3 Y can undergo unusual tandem insertion/cycloaddition/isomerization reactions with diphenyl ketene (Scheme ) . These reactions have proven to be efficient as the key step in the synthesis of the bifunctionalized cyclopentadienyl (C 5 H 3 (C(O)CPh 2 ) 2 ) trianion yttrium complex.…”