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Valence Isomerization in the Solid State: From 1,3-Diphosphacyclobutane-2,4-diyl to 1,2-Dihydro-1,2-diphosphete
Olaf Schmidt1, André Fuchs1, Dietrich Gudat1
1Institut für Anorganische Chemie der Universität, D-53121 Bonn (Germany), Fax: (+49) 228-735-327.
Abstract:
The butadiene-like phosphanylcarbene 2 is, according to ab initio calculations, the intermediate in the conversion of 1 into 3 in the solid state [Eq. (a)]; it is only 1.3 kJ mol-1 higher in energy than 1. For this conversion, only minor changes in the endocyclic bonds are required throughout the entire reaction. R2 N=2,2,6,6-Me4 C5 H6 N.
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Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
Conjugate Addition (1,4-Addition) vs Direct Addition (1,2-Addition)
Conjugate addition results in a thermodynamically stable product. The reaction retains the stronger C=O bond at the expense of the weaker C=C π bond. The process is slow as the β carbon is less electrophilic than the carbonyl carbon.
Direct addition products are...
Valence Bond Theory
Valence Bond Theory

