Metal dihalides

This binuclear photooxidative addition reaction is general for a number of halocarbons (Figure 3). While DCE and 1,2-dibromoethane react cleanly to give the dihalide metal dimers and ethylene, substrates such as bromobenzene or methylene chloride react through an alkyl or aryl intermediate. This intermediate reacts further to yield the dihalide d2-d2 metal complexes. 

Titanium forms dihalides TiXj, for example titanium(II) chloride, formed by heating titanium metal and the tetrachloride to about 1200 K. TiCl2 is a black solid, which disproportionates on standing to TiCl4 + Ti. Since it reduces water to hydrogen, there is no aqueous chemistry for titanium(II). A solid oxide TiO is known. 

Regioselectivity of C—C double bond formation can also be achieved in the reductiv or oxidative elimination of two functional groups from adjacent carbon atoms. Well estab llshed methods in synthesis include the reductive cleavage of cyclic thionocarbonates derivec from glycols (E.J. Corey, 1968 C W. Hartmann, 1972), the reduction of epoxides with Zn/Nal or of dihalides with metals, organometallic compounds, or Nal/acetone (seep.lS6f), and the oxidative decarboxylation of 1,2-dicarboxylic acids (C.A. Grob, 1958 S. Masamune, 1966 R.A. Sheldon, 1972) or their r-butyl peresters (E.N. Cain, 1969). 

In 1975, Weber and Vogtle showed that open-chained polyethers, 2,6-pyridine-dimethanol, and ortho-xylene derivatives terminated in an 8-quinolinyl group could form stable, 1 1, crystalline complexes with a variety of metal salts. The podands were prepared from 8-hydroxyquinoline and the corresponding dihalides. A typical example is shown in Eq. (7.10). 

Lower formal oxidation states are stabilized, however, by M-M bonding in ternary chalcogenides such as M MeQn, M4M6Q13 (M = alkali metal M = Re, Tc Q = S, Se) and the recently reported M gMeS. Their structures are all based on the face-capped, octahedral MeXg cluster unit found in Chevrel phases (p. 1018) and in the dihalides of Mo and W... 

Of the anhydrous dihalides of iron the iodide is easily prepared from the elements but the others are best obtained by passing HX over heated iron. The white (or pale-green) difluoride has the rutile structure the pale-yellow dichloride the CdCl2 structure (based on cep anions, p. 1212) and the yellow-green dibromide and grey diiodide the Cdl2 structure (based on hep anions, p. 1212), in all of which the metal occupies octahedral sites. All these iron dihalides dissolve in water and form crystalline hydrates which may alternatively be obtained by dissolving metallic iron in the aqueous acid. 

The isomorphous diiodides of Ce, Pr and Gd stand apart from all the other, salt-like, dihalides. These three, like LaH, are notable for their metallic lustre and very high conductivities and are best formulated as (Ln ,2I",e", the electron being in a delocalized conduction band. Besides the dihalides, other reduced species have been obtained such as LnsCln (Ln = Sm, Gd, Ho). They have fluorite-related structures (p. 118) in which the anionic sublattice is partially rearranged to accommodate additional anions. 

Infrared spectra and geometry of group II metal dihalides. I. Eliezer and A. Reger, Coord. Chem. Rev., 1972, 9, 189-200 (36). 

Ligand field parameters and spectra of first row transition metal dihalides in the solid state. D. R. Rosseinsky and I. A. Dorrity, Coord. Chem. Rev., 1978, 25, 31-67 (109). 

Scheme 32 Synthesis of metal polysulfido complexes from the corresponding dihalide complexes...

Unlike the di-f dihalides, such compounds differ little in energy from both the equivalent quantity of metal and trihalide, and from other combinations with a similar distribution of metal-metal and metal-halide bonding. So the reduced halide chemistry of the five elements shows considerable variety, and thermodynamics is ill-equipped to account for it. All four elements form di-iodides with strong metal-metal interaction, Prl2 occurring in five different crystalline forms. Lanthanum yields Lai, and for La, Ce and Pr there are hahdes M2X5 where X=Br or I. The rich variety of the chemistry of these tri-f compounds is greatly increased by the incorporahon of other elements that occupy interstitial positions in the lanthanide metal clusters [3 b, 21, 22]. 

Wang, S. G., Schwarz, W. H. E., 1998, Density Functional Study of First Row Transition Metal Dihalides ,... 

Lattice energies of the dihalides of elements of the first transition metal period... 

Eliminations have also been carried out on a number of compounds of the form HalCH2CH2Y, where Y = OH, OR, OCOR, NH2, etc. these eliminations normally require conditions more drastic than for 1,2-dihalides, and metals or metal cations are found to be more effective than Ie. These eliminations are often found to be somewhat indiscriminate in their stereochemistry. The elimination of CO Br6 from the diastereoisomer (72) of 2,3-dibromo-3-phenylpropanoate in Me2CO is, however, found to proceed 100% ANTI, and under extremely mild conditions ... 

Between 1965 and 1969, there were rapid developments in the use of other high temperature species, particularly the silicon dihalides (22-23). boron monofluoride (24), boron atoms (25). silicon atoms (26), and alkali metal atoms (27-28). in reactions at liquid nitrogen temperatures. Clearly this experimental method had to be applied to... 

On the other hand, benzylic polyhalides were converted to the corresponding olefins via vicinal dihalide intermediates. Metallic nickel was also shown to be useful for the dehalogenation of vicinal dihalides(36,43). 

The dihalides of tin and lead behave as ionic metal compounds, and they will not be discussed further. 

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