Bonding in pentalene complexes and their recent applications

Abstract

Molecular orbital (MO) theory is used to describe the bonding in transition metal pentalene complexes in a variety of its coordination modes. The various MO models account for structural parameters and lead to simple rules for electron counting in pentalene complexes. Applications of pentalene complexes in small molecule activation, catalysis and electronic coupling are reported.

Zirconium arene triple-decker sandwich complexes: synthesis, electronic structure and bonding

“…) shows an outstanding ability to stabilise complexes of reactive metal centres, 22,23 particularly when coordinated in Z 8 -mode to an early transition metal or f-element. O'Hare and co-workers have developed the organometallic chemistry of permethylpentalene (C 8 Me 6…”

Single-molecule magnet properties of a monometallic dysprosium pentalene complex

“…, an aromatic bicyclic ligand consisting of two fused C 5 rings. Pentalene coordination chemistry 10 is considerably underdeveloped relative to that of more established π-organometallic ligands such as cyclopentadienide. However, important developments in the synthesis of pentalene pro-ligands have enabled the study of many pentalene complexes, which, in addition to the fundamental interest in their chemistry, have applications in catalysis and small-molecule activation, 11 and as models for metal-containing polymers.…”

“…12 When considered in the context of SMM design, pentalene offers a potential complement to cyclopentadienide and cyclooctatetrenide, the electronic structures of which are regarded as providing axial and equatorial crystal fields, respectively, suitable for slow magnetic relaxation based on dysprosium or erbium, respectively. [6][7][8] In particular, the formal dianionic charge and the η 8 -coordination mode of pentalene, combined with the fold angle between the two fused rings, 10 provide a unique platform on which to construct new magnetic materials. We now describe the SMM properties of [(η 8 -Pn…”

Actinide Organometallic Complexes with π‐Ligands

“…For details of the coordination chemistry of the pentalene ligand please refer to a recent review by Cloke. [30]…”

“…However their role in actinide chemistry is not fully developed yet. For details of the coordination chemistry of the pentalene ligand please refer to a recent review by Cloke …”