Metal-antimony bonds

The magnetic criterion is particularly valuable because it provides a basis for differentiating sharply between essentially ionic and essentially electron-pair bonds Experimental data have as yet been obtained for only a few of the interesting compounds, but these indicate that oxides and fluorides of most metals are ionic. Electron-pair bonds are formed by most of the transition elements with sulfur, selenium, tellurium, phosphorus, arsenic and antimony, as in the sulfide minerals (pyrite, molybdenite, skutterudite, etc.). The halogens other than fluorine form electron-pair bonds with metals of the palladium and platinum groups and sometimes, but not always, with iron-group metals. 

The form of elemental antimony that is stable at normal temperatures and pressures is the gray, metallic rhombohedral a-form, mp 630.7 °C, bp 1587 °C, density 6.70 gcm. Crystals are lustrous. They have a relatively high electrical resistivity (41.7 1 2cm at 20°C). The structure of o -8b consists of sheets of covalently bonded antimony stacked in layers, which are formed of puckered slx-membered rings. Each antimony forms three shorter bonds (2.91 A) in the same layer as well as three longer bonds (3.36 A) to antimony atoms in the adjacent layer. In addition to the a-form, other allotropes include a very unstable yellow form and black forms obtained electrolytically or by condensing the vapor on cold surfaces. Two crystalline allotropes are made by high-pressure techniques. At 85 kbar, a modification with a primitive cubic lattice is formed where each antimony atom is in an octahedral environment of six equidistant (2.96 A) neighbors. Further... 

I.r. and Raman studies have shown the formation of complexes between tributyl phosphate and both arsenic and antimony tribromides. Cryoscopy in fused arsenic tribromide is reported for a num r of inorganic and organic solutes, showing dTj X values lower than the ideal value, and with dioxan the compound 2AsBr3,3dioxan, melting at 64 °C, is formed. Arsenic and antimony trihalides give a-bonded transition-metal derivatives, such as X2E[Fe(CO)2(Cp)]J, where E = As or Sb and X = Cl or Br, on reaction with metal carbonyl anions or metal carbonyls with metal-metal bonds. ... 

Mossbauer spectroscopy has not been noted in this report for some years, so it was of some interest to find that Ishiguro and co-workers have produced Sb, Fe and spectra in a detailed study on antimony-transition metal bonds in metal carbonyl derivatives of tertiary stibines. Finally, in this section, Beyer and Leary comment on energy-resolved collision-induced dissociation of Fc2(CO)/ (y = 1-9). 

Replacement of Labile Chlorines. When PVC is manufactured, competing reactions to the normal head-to-tail free-radical polymerization can sometimes take place. These side reactions are few ia number yet their presence ia the finished resin can be devastating. These abnormal stmctures have weakened carbon—chlorine bonds and are more susceptible to certain displacement reactions than are the normal PVC carbon—chlorine bonds. Carboxylate and mercaptide salts of certain metals, particularly organotin, zinc, cadmium, and antimony, attack these labile chlorine sites and replace them with a more thermally stable C—O or C—S bound ligand. These electrophilic metal centers can readily coordinate with the electronegative polarized chlorine atoms found at sites similar to stmctures (3—6). 

Metallic Antimonides. Numerous binary compounds of antimony with metallic elements are known. The most important of these are indium antimonide [1312-41 -0] InSb, gallium antimonide [12064-03-8] GaSb, and aluminum antimonide [25152-52-7] AlSb, which find extensive use as semiconductors. The alkali metal antimonides, such as lithium antimonide [12057-30-6] and sodium antimonide [12058-86-5] do not consist of simple ions. Rather, there is appreciable covalent bonding between the alkali metal and the Sb as well as between pairs of Na atoms. These compounds are useful for the preparation of organoantimony compounds, such as trimethylstibine [594-10-5] (CH2)2Sb, by reaction with an organohalogen compound. 

Arsenic and antimony are metalloids. They have been known in the pure state since ancient times because they are easily obtained from their ores (Fig. 15.3). In the elemental state, they are used primarily in the semiconductor industry and in the lead alloys used as electrodes in storage batteries. Gallium arsenide is used in lasers, including the lasers used in CD players. Metallic bismuth, with its large, weakly bonded atoms, has a low melting point and is used in alloys that serve as fire detectors in sprinkler systems the alloy melts when a fire breaks out nearby, and the sprinkler system is activated. Like ice, solid bismuth is less dense than the liquid. As a result, molten bismuth does not shrink when it solidifies in molds, and so it is used to make low-temperature castings. 

The structural chemistry of some metal dithiocarbamates, i.e. systematics, coordination modes, crystal packing, and supramolecular self-assembly patterns of nickel, zinc, cadmium, mercury,363 organotin,364 and tellurium,365 366 complexes has been thoroughly analyzed and discussed in detail. Supramolecular self-assembly frequently occurs in non-transition heavier soft metal dithiocarbamates. Thus, lead(II),367 bismuth(III)368 zinc,369 cadmium,370 and (organo)mercury371 dithiocarbamates are associated through M- S secondary bonds, to form either dimeric supermolecules or chain-like supramolecular arrays. The arsenic(III)372 and antimony(III)373 dithiocarbamates are... 

The synthesis of stable complexes with transition metal-phosphorus triple bonds is of fundamental importance and opens a novel chapter of a special field of coordination chemistry. The synthesis of analogous complexes with ligands of the heavier homologues like arsenic has partially been carried out [6], while for antimony and bismuth, the elusive M=Sb and M=Bi systems have now moved within reach. Moreover, the experimental and theoretical... 

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