In chemistry, a metallophilic interaction is defined as a type of non-covalent attraction between heavy metal atoms. The atoms are often within Van der Waals distance of each other and are about as strong as hydrogen bonds. [1] The effect can be intramolecular or intermolecular. Intermolecular metallophilic interactions can lead to formation of supramolecular assemblies whose properties vary with the choice of element and oxidation states of the metal atoms and the attachment of various ligands to them. [2]
The nature of such interactions remains the subject of vigorous debate with recent studies emphasizing that the metallophilic interaction is repulsive due to strong metal-metal Pauli exclusion principle repulsion. [3]
Previously, this type of interaction was considered to be enhanced by relativistic effects. A major contributor is electron correlation of the closed-shell components, [2] which is unusual because closed-shell atoms generally have negligible interaction with one another at the distances observed for the metal atoms. As a trend, the effect becomes larger moving down a periodic table group, for example, from copper to silver to gold, in keeping with increased relativistic effects. [2] Observations and theory find that, on average, 28% of the binding energy in gold–gold interactions can be attributed to relativistic expansion of the gold d orbitals. [4]
Recently, the relativistic effect was found to enhance the intermolecular M-M Pauli repulsion of the closed-shell organometallic complexes. [3] At close M–M distances, metallophilicity is repulsive in nature due to strong M–M Pauli repulsion. The relativistic effect facilitates (n + 1)s-nd and (n + 1)p-nd orbital hybridization of the metal atom, where (n + 1)s-nd hybridization induces strong M–M Pauli repulsion and repulsive M–M orbital interaction, and (n + 1)p-nd hybridization suppresses M–M Pauli repulsion. This model is validated by both DFT (density functional theory) and high-level CCSD(T) (coupled-cluster singles and doubles with perturbative triples) computations. [3]
An important and exploitable property of aurophilic interactions relevant to their supramolecular chemistry is that while both inter- and intramolecular interactions are possible, intermolecular aurophilic linkages are comparatively weak and the gold–gold bonds are easily broken by solvation; most complexes that exhibit intramolecular aurophilic interactions retain such moieties in solution. [5] One way of probing the strength of particular intermolecular metallophilic interactions is to use a competing solvent and examine how it interferes with supromolecular properties. For example, adding various solvents to gold(I) nanoparticles whose luminescence is attributed to Au–Au interactions will have decreasing luminescence as the solvent disrupts the metallophilic interactions. [5]
The polymerization of metal atoms can lead to the formation of long chains or nucleated clusters. Gold nanoparticles formed from chains of gold(I) complexes linked by aurophilic interactions often give rise to intense luminescence in the visible region of the spectrum. [5]
Chains of Pd(II)–Pd(I) and Pt(II)–Pd(I) complexes have been explored as potential molecular wires. [6]
A chemical bond is the association of atoms or ions to form molecules, crystals, and other structures. The bond may result from the electrostatic force between oppositely charged ions as in ionic bonds or through the sharing of electrons as in covalent bonds, or some combination of these effects. Chemical bonds are described as having different strengths: there are "strong bonds" or "primary bonds" such as covalent, ionic and metallic bonds, and "weak bonds" or "secondary bonds" such as dipole–dipole interactions, the London dispersion force, and hydrogen bonding.
Ionic bonding is a type of chemical bonding that involves the electrostatic attraction between oppositely charged ions, or between two atoms with sharply different electronegativities, and is the primary interaction occurring in ionic compounds. It is one of the main types of bonding, along with covalent bonding and metallic bonding. Ions are atoms with an electrostatic charge. Atoms that gain electrons make negatively charged ions. Atoms that lose electrons make positively charged ions. This transfer of electrons is known as electrovalence in contrast to covalence. In the simplest case, the cation is a metal atom and the anion is a nonmetal atom, but these ions can be more complex, e.g. molecular ions like NH+
4 or SO2−
4. In simpler words, an ionic bond results from the transfer of electrons from a metal to a non-metal to obtain a full valence shell for both atoms.
An intermolecular force is the force that mediates interaction between molecules, including the electromagnetic forces of attraction or repulsion which act between atoms and other types of neighbouring particles, e.g. atoms or ions. Intermolecular forces are weak relative to intramolecular forces – the forces which hold a molecule together. For example, the covalent bond, involving sharing electron pairs between atoms, is much stronger than the forces present between neighboring molecules. Both sets of forces are essential parts of force fields frequently used in molecular mechanics.
In quantum mechanics, the Pauli exclusion principle states that two or more identical particles with half-integer spins cannot simultaneously occupy the same quantum state within a system that obeys the laws of quantum mechanics. This principle was formulated by Austrian physicist Wolfgang Pauli in 1925 for electrons, and later extended to all fermions with his spin–statistics theorem of 1940.
Solvation describes the interaction of a solvent with dissolved molecules. Both ionized and uncharged molecules interact strongly with a solvent, and the strength and nature of this interaction influence many properties of the solute, including solubility, reactivity, and color, as well as influencing the properties of the solvent such as its viscosity and density. If the attractive forces between the solvent and solute particles are greater than the attractive forces holding the solute particles together, the solvent particles pull the solute particles apart and surround them. The surrounded solute particles then move away from the solid solute and out into the solution. Ions are surrounded by a concentric shell of solvent. Solvation is the process of reorganizing solvent and solute molecules into solvation complexes and involves bond formation, hydrogen bonding, and van der Waals forces. Solvation of a solute by water is called hydration.
In molecular physics and chemistry, the van der Waals force is a distance-dependent interaction between atoms or molecules. Unlike ionic or covalent bonds, these attractions do not result from a chemical electronic bond; they are comparatively weak and therefore more susceptible to disturbance. The van der Waals force quickly vanishes at longer distances between interacting molecules.
In chemistry, a lone pair refers to a pair of valence electrons that are not shared with another atom in a covalent bond and is sometimes called an unshared pair or non-bonding pair. Lone pairs are found in the outermost electron shell of atoms. They can be identified by using a Lewis structure. Electron pairs are therefore considered lone pairs if two electrons are paired but are not used in chemical bonding. Thus, the number of electrons in lone pairs plus the number of electrons in bonds equals the number of valence electrons around an atom.
Valence shell electron pair repulsion (VSEPR) theory is a model used in chemistry to predict the geometry of individual molecules from the number of electron pairs surrounding their central atoms. It is also named the Gillespie-Nyholm theory after its two main developers, Ronald Gillespie and Ronald Nyholm.
In chemistry, π backbonding is a π-bonding interaction between a filled (or half filled) orbital of a transition metal atom and a vacant orbital on an adjacent ion or molecule. In this type of interaction, electrons from the metal are used to bond to the ligand, which dissipates excess negative charge and stabilizes the metal. It is common in transition metals with low oxidation states that have ligands such as carbon monoxide, olefins, or phosphines. The ligands involved in π backbonding can be broken into three groups: carbonyls and nitrogen analogs, alkenes and alkynes, and phosphines. Compounds where π backbonding is prominent include Ni(CO)4, Zeise's salt, and molybdenum and iron dinitrogen complexes.
Relativistic quantum chemistry combines relativistic mechanics with quantum chemistry to calculate elemental properties and structure, especially for the heavier elements of the periodic table. A prominent example is an explanation for the color of gold: due to relativistic effects, it is not silvery like most other metals.
In chemistry, a non-covalent interaction differs from a covalent bond in that it does not involve the sharing of electrons, but rather involves more dispersed variations of electromagnetic interactions between molecules or within a molecule. The chemical energy released in the formation of non-covalent interactions is typically on the order of 1–5 kcal/mol. Non-covalent interactions can be classified into different categories, such as electrostatic, π-effects, van der Waals forces, and hydrophobic effects.
In organic chemistry, the anomeric effect or Edward-Lemieux effect is a stereoelectronic effect that describes the tendency of heteroatomic substituents adjacent to a heteroatom within a cyclohexane ring to prefer the axial orientation instead of the less-hindered equatorial orientation that would be expected from steric considerations. This effect was originally observed in pyranose rings by J. T. Edward in 1955 when studying carbohydrate chemistry.
In chemistry, aurophilicity refers to the tendency of gold complexes to aggregate via formation of weak metallophilic interactions.
In organic chemistry, hydroamination is the addition of an N−H bond of an amine across a carbon-carbon multiple bond of an alkene, alkyne, diene, or allene. In the ideal case, hydroamination is atom economical and green. Amines are common in fine-chemical, pharmaceutical, and agricultural industries. Hydroamination can be used intramolecularly to create heterocycles or intermolecularly with a separate amine and unsaturated compound. The development of catalysts for hydroamination remains an active area, especially for alkenes. Although practical hydroamination reactions can be effected for dienes and electrophilic alkenes, the term hydroamination often implies reactions metal-catalyzed processes.
In chemistry, π-effects or π-interactions are a type of non-covalent interaction that involves π systems. Just like in an electrostatic interaction where a region of negative charge interacts with a positive charge, the electron-rich π system can interact with a metal, an anion, another molecule and even another π system. Non-covalent interactions involving π systems are pivotal to biological events such as protein-ligand recognition.
Organogold chemistry is the study of compounds containing gold–carbon bonds. They are studied in academic research, but have not received widespread use otherwise. The dominant oxidation states for organogold compounds are I with coordination number 2 and a linear molecular geometry and III with CN = 4 and a square planar molecular geometry.
In chemistry, a crossover experiment is a method used to study the mechanism of a chemical reaction. In a crossover experiment, two similar but distinguishable reactants simultaneously undergo a reaction as part of the same reaction mixture. The products formed will either correspond directly to one of the two reactants or will include components of both reactants. The aim of a crossover experiment is to determine whether or not a reaction process involves a stage where the components of each reactant have an opportunity to exchange with each other.
In the theory of chemical reactivity, the Klopman–Salem equation describes the energetic change that occurs when two species approach each other in the course of a reaction and begin to interact, as their associated molecular orbitals begin to overlap with each other and atoms bearing partial charges begin to experience attractive or repulsive electrostatic forces. First described independently by Gilles Klopman and Lionel Salem in 1968, this relationship provides a mathematical basis for the key assumptions of frontier molecular orbital theory and hard soft acid base (HSAB) theory. Conceptually, it highlights the importance of considering both electrostatic interactions and orbital interactions when rationalizing the selectivity or reactivity of a chemical process.
Plumbylenes (or plumbylidenes) are divalent organolead(II) analogues of carbenes, with the general chemical formula, R2Pb, where R denotes a substituent. Plumbylenes possess 6 electrons in their valence shell, and are considered open shell species.
Dispersion stabilized molecules are molecules where the London dispersion force (LDF), a non-covalent attractive force between atoms and molecules, plays a significant role in promoting the molecule's stability. Distinct from steric hindrance, dispersion stabilization has only recently been considered in depth by organic and inorganic chemists after earlier gaining prominence in protein science and supramolecular chemistry. Although usually weaker than covalent bonding and other forms of non-covalent interactions like hydrogen bonding, dispersion forces are known to be a significant if not dominating stabilizing force in certain organic, inorganic, and main group molecules, stabilizing otherwise reactive moieties and exotic bonding.
| Intramolecular (strong) |
|    | ||||||
|---|---|---|---|---|---|---|---|---|
| Intermolecular (weak) |
| |||||||
| Bond cleavage | ||||||||
| Electron counting rules | ||||||||