Diamagnetic molecules

Pacaiilt, Horau, and Marchand have ven a review of the experimental and theoretical work concerning the diamagnetic properties of molecules. Diamagnetic anisotropy of electron groups is reviewed by Bothner-By and Pople. ... 

Write the ground-state electron configuration for B2. Is the molecule diamagnetic or paramagnetic ... 

Fig. 4 Cartoon representation of EPR distance measurements, (a) Doubly labeled monomeric proteins give rise to intra- and intermolecular spin-spin interactions. In order to determine intramolecular distances, experimental data has to be corrected for intermolecular contributions, (b) Intermolecular distance measurements using singly labeled proteins in protein oligomers or aggregates. Multiples of the distance are also expected. This may be even more complicated for different types of aggregation and can be analyzed by studying a series of samples with increasing content of non-labeled molecules (diamagnetic dilution), (c) To measure intramolecular distances within oligomers/aggregates, a mixture of doubly labeled and non-labeled proteins can be used...

EXERCISE 10.10 Give the orbital diagram and electron configuration for the carbon monoxide molecule, CO. What is the bond order of CO Is the molecule diamagnetic or paramagnetic ... 

CIDNP involves the observation of diamagnetic products fonned from chemical reactions which have radical intemiediates. We first define the geminate radical pair (RP) as the two molecules which are bom in a radical reaction with a well defined phase relation (singlet or triplet) between their spins. Because the spin physics of the radical pair are a fiindamental part of any description of the origins of CIDNP, it is instmctive to begin with a discussion of the radical-pair spin Hamiltonian. The Hamiltonian can be used in conjunction with an appropriate basis set to obtain the energetics and populations of the RP spin states. A suitable Hamiltonian for a radical pair consisting of radicals 1 and 2 is shown in equation (B1.16.1) below [12]. 

Unlike nitrogen monoxide, nitrogen dioxide has properties more typical of an odd electron molecule. It is a coloured (brown), reactive gas which dimerises to the diamagnetic colourless gas dinitrogen tetroxide, N2O4. in which the odd electron is paired. The structure of dinitrogen tetroxide can be represented as a resonance hybrid of ... 

Prussian Blue. Reaction of [Fe(CN)3] with an excess of aqueous h on(Ill) produces the finely divided, intensely blue precipitate Pmssian Blue [1403843-8] (tetrairon(Ill) tris(hexakiscyanoferrate)), Fe4[Fe(CN)3]. Pmssian Blue is identical to Turnbull s Blue, the name which originally was given to the material produced by reaction of [Fe(CN)3] with excess aqueous h on(Il). The soHd contains or has absorbed on its surface a large and variable number of water molecules, potassium ions (if present in the reaction), and h on(Ill) oxide. The h on(Il) centers are low spin and diamagnetic h on(Ill) centers are high spin. Variations of composition and properties result from variations in reaction conditions. Rapid precipitation in the presence of potassium ion affords a colloidal suspension of Pmssian Blue [25869-98-1] which has the approximate composition KFe[Fe(CN)3]. Pmssian Blue compounds are used as pigments in inks and paints and its formation on sensitized paper is utilized in the production of blueprints. 

The neutral complexes of chromium, molybdenum, tungsten, and vanadium are six-coordinate and the CO molecules are arranged about the metal in an octahedral configuration as shown in stmcture (3). Vanadium carbonyl possesses an unpaired electron and would be expected to form a metal—metal bond. Steric hindrance may prevent dimerization. The other hexacarbonyls are diamagnetic. 

Most of the free-radical mechanisms discussed thus far have involved some combination of homolytic bond dissociation, atom abstraction, and addition steps. In this section, we will discuss reactions that include discrete electron-transfer steps. Addition to or removal of one electron fi om a diamagnetic organic molecule generates a radical. Organic reactions that involve electron-transfer steps are often mediated by transition-metal ions. Many transition-metal ions have two or more relatively stable oxidation states differing by one electron. Transition-metal ions therefore firequently participate in electron-transfer processes. 

Planar-octahedral equilibria. Dissolution of planar Ni compounds in coordinating solvents such as water or pyridine frequently leads to the formation of octahedral complexes by the coordination of 2 solvent molecules. This can, on occasions, lead to solutions in which the Ni has an intermediate value of jie indicating the presence of comparable amounts of planar and octahedral molecules varying with temperature and concentration more commonly the conversion is complete and octahedral solvates can be crystallized out. Well-known examples of this behaviour are provided by the complexes [Ni(L-L)2X2] (L-L = substituted ethylenediamine, X = variety of anions) generally known by the name of their discoverer I. Lifschitz. Some of these Lifschitz salts are yellow, diamagnetic and planar, [Ni(L-L)2]X2, others are blue, paramagnetic, and octahedral, [Ni(L-L)2X2] or... 

A major weakness of valence bond theory has been its inability to predict the magnetic properties of molecules. We mentioned this problem in Chapter 7 with regard to the 02 molecule, which is paramagnetic, even though it has an even number (12) of valence electrons. The octet rule, or valence bond theory, would predict that all the electrons in 02 should be paired, which would make it diamagnetic. 

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