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Mass Spectrometry: Alkyl Halide Fragmentation

Mass Spectrometry: Alkyl Halide Fragmentation

Chlorine isotopes exist as 35Cl and 37Cl in a 3:1 ratio, while bromine isotopes exist as 79Br and 81Br in a 1:1 ratio. The mass spectrum of alkyl halides typically produces two distinct molecular ion peaks, the molecular ion peak, [M], and the molecular ion plus two, [M + 2] peak. The relative heights of these two peaks are proportional to the isotopic abundance ratios of the halide. For example, 2‐chloropropane and 1‐bromopropane display two peaks with relative peak heights in a 3:1 and 1:1...

Halogens

Halogens

Group 17 elements, known as halogens, are nonmetals. At room temperature, fluorine and chlorine are gases, bromine is a liquid, and iodine a solid. Astatine is a highly unstable radioactive element, so currently, most of its properties are unknown due to its short half-life. Tennessine is a synthetic element also predicted to be in this group.

Halogenation of Alkenes

Halogenation of Alkenes

Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.

Hybridization of Atomic Orbitals II

Hybridization of Atomic Orbitals II

sp3d and sp3d 2 Hybridization

Alkyl Halides

Alkyl Halides

Structural Properties
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...

Hybridization of Atomic Orbitals I

Hybridization of Atomic Orbitals I

The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...

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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

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Evolution of superhalogen properties in PtCl(n) clusters.

Jorly Joseph¹, Kalpataru Pradhan, Purusottam Jena

¹Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284, USA.

The Journal of Chemical Physics

|May 23, 2012

Summary

Platinum-chlorine clusters exhibit covalent bonding, with unique binding behaviors in larger neutral and anionic forms. These clusters, particularly PtCl(n) for n≥3, function as superhalogens, confirmed by photoelectron spectroscopy.

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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates

Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates

Published on: February 15, 2016

Area of Science:

Computational chemistry
Materials science
Quantum mechanics

Background:

Understanding the electronic and structural properties of transition metal clusters is crucial for developing new materials.
Platinum-chlorine clusters are of interest due to their potential catalytic and electronic applications.

Purpose of the Study:

To systematically investigate the ground-state geometries, stability, electronic structure, and spectroscopic properties of platinum-chlorine (PtCln) clusters (n=1-7).
To explore the transition from atomic to molecular chlorine binding in these clusters.
To determine the electron affinity and superhalogen characteristics of PtCln clusters.

Main Methods:

Systematic theoretical calculations of ground-state geometries and electronic structures.
Analysis of relative stability and bonding characteristics.
Comparison with experimental photoelectron spectroscopy data for validation.

Main Results:

Covalent bonding dominates PtCln clusters, with distinct chemical binding of chlorine atoms up to n=5 in neutral clusters.
Neutral PtCl6 and PtCl7, and anionic PtCl7 exhibit molecular chlorine binding.
PtCln clusters (n≥3) are identified as superhalogens with high electron affinities, peaking at 5.81 eV for PtCl5.
Cluster geometries resemble octahedral fragments, stabilized by d-orbital splitting.

Conclusions:

The study provides a comprehensive theoretical understanding of PtCln cluster properties.
Experimental validation confirms the calculated electronic and structural characteristics.
PtCln clusters demonstrate significant potential as superhalogen materials.