Publication

Speciation of Bulky Chiral Cyclopentadienyl Cobalt(III) Complexes: Isolation of Air-Stable 16-Electron Species

2026

Abstract

Bulky pentasubstituted chiral cyclopentadienyl ligands (Cp V ) were shown to form distinct species upon cobalt(III) complexation, which differ in the nature and number of auxiliary ligands. Aside from the well-established coordinatively saturated Cp V Co(CO)I 2 architecture and its dimeric [Cp V CoI 2 ] 2 derivative, the formation of monomeric 16-electron species of type Cp V CoI 2 was confirmed as well, thus representing a rare example of air-stable chiral half-sandwich complexes with an unsaturated 3d-metal center. Herein, we report the isolation and structural characterization of these organometallic species, of which the dominant coordination mode depends on the steric encumbrance of the employed Cp V ligand. Addition of a two-electron donor ligand, such as carbon monoxide or an isocyanide, showed that the unsaturated complexes can be converted back to 18-electron adducts.

Official source

https://infoscience.epfl.ch/entities/publication/3feefbc6-cc0b-4111-939e-a60d330f4269

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2026

Abstract

Official source

https://infoscience.epfl.ch/entities/publication/3feefbc6-cc0b-4111-939e-a60d330f4269

About this result

Related concepts (32)

18-electron rule

The 18-electron rule is a chemical rule of thumb used primarily for predicting and rationalizing formulas for stable transition metal complexes, especially organometallic compounds. The rule is based on the fact that the valence orbitals in the electron configuration of transition metals consist of five (n−1)d orbitals, one ns orbital, and three np orbitals, where n is the principal quantum number. These orbitals can collectively accommodate 18 electrons as either bonding or non-bonding electron pairs.

Ligand

In coordination chemistry, a ligand is an ion or molecule with a functional group that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electron pairs, often through Lewis bases. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands".

Metal–ligand multiple bond

In organometallic chemistry, a metal–ligand multiple bond describes the interaction of certain ligands with a metal with a bond order greater than one. Coordination complexes featuring multiply bonded ligands are of both scholarly and practical interest. Transition metal carbene complexes catalyze the olefin metathesis reaction. Metal oxo intermediates are pervasive in oxidation catalysis. As a cautionary note, the classification of a metal ligand bond as being "multiple" bond order is ambiguous and even arbitrary because bond order is a formalism.