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Valence Bond Theory

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...

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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.
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For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.

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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...

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Ladder Diagrams: Complexation Equilibria

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Ladder diagrams are useful for evaluating equilibria involving metal-ligand complexes. The vertical scale of the ladder diagram represents the concentration of unreacted or free ligand, pL. The horizontal lines on the scale depict the log of stepwise formation constants for metal-ligand complexes and indicate the dominant species in all the regions.
The formation constant, K1, for the formation of Cd(NH3)2+ complex from cadmium and ammonia is 3.55 × 102. Log K1 (i.e. pNH3) is 2.55, and...

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Updated: Nov 12, 2025

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI

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Published on: November 22, 2016

M/X Phosphinidenoid Metal Complex Chemistry.

Alexander Schmer¹, Philip Junker¹, Arturo Espinosa Ferao²

¹Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.

Accounts of Chemical Research

|March 18, 2021

Summary

Transient nucleophilic phosphinidenoid complexes offer a versatile P1 building block alternative to electrophilic phosphinidenes. Their facile synthesis and broad reactivity enable access to novel organophosphorus compounds and strained heterocyclic ligands.

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Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI

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Published on: November 22, 2016

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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Published on: April 10, 2015

Area of Science:

Organometallic Chemistry
Synthetic Chemistry
Computational Chemistry

Background:

Electrophilic terminal phosphinidene complexes are useful but difficult to synthesize.
Nucleophilic M/Cl phosphinidenoid complexes are easily accessible in one step.
These complexes serve as valuable P1 building blocks for novel compounds.

Purpose of the Study:

To describe the chemistry of nucleophilic M/Cl phosphinidenoid complexes.
To explore their synthetic applicability and reactivity patterns.
To provide insights into bonding and mechanistic aspects via DFT calculations.

Main Methods:

One-step synthesis of M/Cl phosphinidenoid complexes from [M(CO)x(RPCl2)].
Solution-phase NMR spectroscopy and solid-state X-ray diffraction for characterization.
High-level density functional theory (DFT) calculations for mechanistic studies.

Main Results:

Established prerequisites for complex formation and usability (steric demand, metal complexation, solvent, crown ether).
Identified diverse reactivity: self-condensations, electrophilic/nucleophilic reactions, 1,1-additions, [2+1] cycloadditions, ring expansions, and redox reactions.
Demonstrated synthesis of strained P-heterocyclic ligands (oxaphosphiranes, azaphosphiridines, 1,2-oxaphosphetanes, 1,2-thiaphosphetanes) and novel organophosphorus compounds.

Conclusions:

Nucleophilic phosphinidenoid complexes are versatile P1 synthons with broad applicability.
Their reactivity enables access to diverse organophosphorus compounds and valuable heterocyclic ligands.
This chemistry expands understanding of bonding and reactivity, opening new avenues in organoelement chemistry.