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Metal-Ligand Bonds

Metal-Ligand Bonds

The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...

Formation of Complex Ions

Formation of Complex Ions

A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...

Ligand Binding Sites

Ligand Binding Sites

Proteins are dynamic macromolecules that carry out a wide variety of essential processes; however, the activities of most proteins depend on their interactions with other molecules or ions, known as ligands.
Protein-ligand interactions are quite specific; even though numerous potential ligands surround a cellular protein at any given time, only a particular ligand can bind to that protein. Moreover, a ligand binds only to a dedicated area on the surface of the protein, known as the...

Ligand Binding and Linkage

Ligand Binding and Linkage

Allosteric proteins have more than one ligand binding site; the binding of a ligand to any of these sites influences the binding of ligands to the other sites. When a protein is allosteric, its binding sites are called coupled or linked. In the case of enzymes, the site that binds to the substrate is known as the active site and the other site is known as the regulatory site. When a ligand binds to the regulatory site, this leads to conformational changes in the protein that can influence...

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...

Trigonometric Substitution

Trigonometric Substitution

Trigonometric substitution is a technique used to simplify integrals that contain square root expressions involving quadratic forms. It is particularly effective when the integrand includes terms resembling those found in standard geometric equations, such as circles or ellipses.Molniya satellites follow highly elliptical orbits, repeatedly sweeping out the same regions of space as they revolve around Earth. To estimate the area enclosed by such an orbit, the path is modeled as an ellipse...

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Related Experiment Video

Updated: Feb 10, 2026

Assessing the Autonomic and Behavioral Effects of Passive Motion in Rats using Elevator Vertical Motion and Ferris-Wheel Rotation

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Published on: February 7, 2020

Rotational Behavior in Piano Stool Ru(II) Complexes with Bulky-Substituted Cyclopentadienyl Ligands.

Naoki Ito¹, Toshio Nishino¹, Jérôme Cuny²

¹Division of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma 630-0192, Japan.

ACS Organic & Inorganic Au

|February 9, 2026

Summary

Novel piano stool ruthenium complexes with bulky substituents were synthesized. These bulky groups increase the rotational barrier around the cyclopentadienyl-ruthenium bond, paving the way for ambient temperature molecular motors.

Keywords:

cyclopentadienyl ligand molecular machine molecular rotor piano stool complex ruthenium

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Analyzing Protein Architectures and Protein-Ligand Complexes by Integrative Structural Mass Spectrometry

Analyzing Protein Architectures and Protein-Ligand Complexes by Integrative Structural Mass Spectrometry

Published on: October 15, 2018

Area of Science:

Organometallic Chemistry
Molecular Machines

Background:

Piano stool ruthenium complexes are key components in molecular machinery.
Controlling rotational dynamics in organometallic complexes is crucial for developing functional molecular motors.

Purpose of the Study:

To investigate the effect of bulky substituents on the cyclopentadienyl (Cp) ligand on the rotational behavior around the Cp-Ru bond in piano stool ruthenium complexes.
To design and synthesize novel ruthenium complexes with sterically demanding Cp substituents to increase rotational barriers.

Main Methods:

Synthesis of novel piano stool ruthenium complexes with m-xylyl, mesityl, and 9-anthracenyl substituted Cp ligands.
Nuclear Magnetic Resonance (NMR) spectroscopy to study rotational dynamics.
Variable-temperature NMR measurements and line shape fitting analysis to determine activation free energy (ΔG‡).
Theoretical calculations to confirm experimental findings and analyze transition states.

Main Results:

Complexes with mesityl and 9-anthracenyl substituents exhibited significantly higher activation free energies (69.5 and 67.8 kJ mol⁻¹, respectively) for Cp rotation compared to a previously reported pentaphenyl Cp complex (18.9 kJ mol⁻¹).
The m-xylyl substituted complex showed rotation faster than the NMR time scale.
Activation enthalpy was identified as the primary contributor to the increased rotational barrier, attributed to steric hindrance between bulky Cp substituents and the tripodal ligand.

Conclusions:

Bulky substituents on the Cp ligand effectively increase the rotational barrier around the Cp-Ru bond by occupying the spatial gap within the tripodal ligand.
These findings provide valuable insights for designing single-molecule magnet (SMM)-operable molecular motors capable of functioning at ambient temperatures.
The study demonstrates a strategy to enhance the stability and functionality of molecular motors by controlling rotational dynamics through steric effects.