Ethers atomic charges

What effect does the solvent have on the structure, charges and reactivity of Grignards Compare geometries, atomic charges and electrostatic potential maps of the diethyl ether complex to that of methylmagnesium chloride itself. How does solvent-magnesium bond formation affect the reactivity of the methyl group Explain. 

For the parent aUyl vinyl ether, solvent effects on the rate of the Claisen rearrangement were studied computationally by Davidson and Hillier applying a number of variants of the continuum model [39]. The authors found that on the RHF/6-31G level, the polarizable continuum model (PCM) was most successful in predicting the barrier lowering in di-n-butyl ether and water. Based on calculated atomic charges and the dipole moment, the authors concluded that, "... there is considerably more electron polarization in the transition state than in the ground state... ... 

Crown ethers are macrocyclic poly ethers, forming charged metal ion complexes by ion-dipole interactions. These complexes, with an appropriate counter-ion, are usually soluble in organic solvents. A simple example is dicyclohexyl-18-crown-6 (18 atoms in the ring, 6 heterocyclic oxygen atoms). 

Uranium tetrachloride [10026-10-5], UCl, has been prepared by several methods. The first method, which is probably the best, involves the reduction/chlorination of UO [1344-58-7] with boiling hexachloropropene. The second consists of heating UO2 [1344-57-6] under flowing CCl or SOCI2. The stmcture of the dark green tetrachloride is identical to that of Th, Pa, and Np, which all show a dodecahedral geometry of the chlorine atoms about a central actinide metal atom. The tetrachloride is soluble in H2O, alcohol, and acetic acid, but insoluble in ether, and chloroform. Industrially the tetrachloride has been used as a charge for calutrons. 

Zinc-Copper Couple A 500-ml Erlenmeyer flask equipped for magnetic stirring is charged with a mixture of zinc powder (49.2 g, 0.75 g-atom) and hydrochloric acid (40 ml of 3 % aqueous solution). The contents of the flask are rapidly stirred for 1 minute, and the liquid is decanted. Similarly, the zinc is washed with the following three times with 40 ml of 3% hydrochloric acid solution, five times with 100 ml of distilled water, five times with 75 ml of 2 % aqueous copper sulfate solution, five times with 100 ml of distilled water, four times with 100 ml of absolute ethanol, and five times with 100 ml of absolute ether. These last ethanol and ether washes are decanted onto a Buchner funnel to prevent loss. The residue is collected by suction filtration, washed again with anhydrous ether, and dried in air. Finally, the zinc-copper couple is stored (20-24 hours) in a vacuum desiccator over phosphorous pentoxide. 

Zollinger and coworkers (Nakazumi et al., 1983) therefore supposed that the diazonium ion and the crown ether are in a rapid equilibrium with two complexes as in Scheme 11-2. One of these is the charge-transfer complex (CT), whose stability is based on the interaction between the acceptor (ArNj) and donor components (Crown). The acceptor center of the diazonium ion is either the (3-nitrogen atom or the combined 7r-electron system of the aryl part and the diazonio group, while the donor centers are one or more of the ether oxygen atoms. The other partner in the equilibrium is the insertion complex (IC), as shown in structure 11.5. Scheme 11-2 is intended to leave the question open as to whether the CT and IC complexes are formed competitively or consecutively from the components. ... 

Laali and Lattimer (1989 see also Laali, 1990) observed arenediazonium ion/crown ether complexes in the gas phase by field desorption (FD) and by fast atom bombardment (FAB) mass spectrometry. The FAB-MS spectrum of benzenediazonium ion/18-crown-6 shows a 1 1 complex. In the FD spectrum, apart from the 1 1 complex, a one-cation/two-crown complex is also detected. Dicyclo-hexano-24-crown-6 appears to complex readily in the gas phase, whereas in solution this crown ether is rather poor for complexation (see earlier in this section) the presence of one or three methyl groups in the 2- or 2,4,6-positions respectively has little effect on the gas-phase complexation. With 4-nitrobenzenediazonium ion, 18-crown-6 even forms a 1 3 complex. The authors assume charge-transfer complexes such as 11.13 for all these species. There is also evidence for hydride ion transfer from the crown host within the 1 1 complex, and for either the arenediazonium ion or the aryl cation formed from it under the reaction conditions in the gas phase in tandem mass spectrometry (Laali, 1990). 

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