Anionic trimers

Photoelectron spectroscopy has been performed on [Sb ] and [Bi ] cluster anions with photon energies of 4.03 eV and in some cases S.OeV [100], For the small clusters, density functional theory calculations of the detachment energies are presented. The geometric structures of the small anionic antimony and bismuth clusters are similar, and similar to those of other group 15 elements. For the neutral and anionic trimers nonlinear geometries, in particular Jahn-Teller-distorted triangles were obtained. 

The tetramer exists in two-molal zirconium chloride and nitrate solutions, but it polymerizes into cross-linked chains on hydrolysis (190—191) in strong acid solutions, the hydroxyl bridges can be replaced by other anions to form trimers (192) and monomers (192—193). 

The most important reaction with Lewis acids such as boron trifluoride etherate is polymerization (Scheme 30) (72MI50601). Other Lewis acids have been used SnCL, Bu 2A1C1, Bu sAl, Et2Zn, SO3, PFs, TiCU, AICI3, Pd(II) and Pt(II) salts. Trialkylaluminum, dialkylzinc and other alkyl metal initiators may partially hydrolyze to catalyze the polymerization by an anionic mechanism rather than the cationic one illustrated in Scheme 30. Cyclic dimers and trimers are often products of cationic polymerization reactions, and desulfurization of the monomer may occur. Polymerization of optically active thiiranes yields optically active polymers (75MI50600). 

Figure 13.14 Schematic representation of the structure of (a) the trimeric anion [Sb.iFi203l, and (b) the dimeric anion fAs2F

NaAs03 has an infinite polymeric chain anion similar to that in diopside (pp. 349, 529) but with a trimeric repeat unit LiAs03 is similar but with a dimeric repeat unit whereas /6-KASO3 appears to have a cyclic trimeric anion As309 which resembles the cyc/o-trimetaphosphates (p. 530). There is thus a certain structural similarity between arsenates and phosphates, though arsenic acid and the arsenates show less tendency to catenation (p. 526). The tetrahedral As 04) group also resembles PO4) in forming the central unit in several heteropoly acid anions (p. 1014). 

An alternate way to make block copolymers involving PDMS blocks 124,125) is to have these chains fitted with epoxide functions at chain end, and to react them with a vinylic or dienic polymer carrying terminal COOH functions. Sequential addition of monomers has also been used, the ring opening polymerization of the cyclic trimer (D3) being initiated by the anionic site of a living polymer126). 

Kuznetsov and Boldyrev [15] provided theoretical evidence that the 33 , Al3 , and Ga3 anions (lOe) have geometrical (cyclic, planar) and electronic (two delocalized 7t electrons) properties to be considered as aromatic systems. Positive cations of all group XV trimers (14e), P3 " As3 Sb3 and Bi3+, have equilateral-triangular ground states [16]. 

Silicagel. Silicagel is usually prepared from sodium silicates, which are produced as glasses with a stoichiometry of Si02/Na20 = 0.6-0.25. At the right pH they arc soluble in water and the solution contains mixtures of silicate anions monomeric, dimeric, trimeric species, etc. (Fig. 3.13). 

There is little mention in the literature of the use of amide salts in substitution reactions on chlorophosphazene precursors. The anilide anion was shown to be a powerful nucleophile in substitution reactions on various trimer derivatives, but investigations of such reactions with the high polymer have not been reported.22 Where strong nucleophiles (such as amide salts) with low steric requirements are employed, the usual pentacoordinate transition state (Scheme 1), may be a viable reaction intermediate which can undergo alternative modes of decomposition, perhaps involving chain cleavage and/or cross-linking. 

Various polyphosphates are effective sequestering agents under appropriate conditions. The best known of these is sodium hexametaphosphate (10.14), the cyclic hexamer of sodium orthophosphate. Further examples are the cyclic trimer sodium trimetaphosphate (10.15), as well as the dimeric pyrophosphate (10.16), the trimeric tripolyphosphate (10.17) and other linear polyphosphates (10.18). All of these polyanions function by withdrawing the troublesome metal cation into an innocuous and water-soluble complex anion by a process of ion exchange as shown in Scheme 10.7 for sodium hexametaphosphate. Hence these compounds are sometimes referred to as ion-exchange agents. 

The P3093 ion (known as the trimetaphosphate ion) and (S03)3, a trimer of S03, also have this structure. The trimetaphosphate ion can be considered as the anion of the acid H3P309 (trimetaphos-phoric acid), a trimeric form of HP03 (metaphosphoric acid). Note that this acid is formally related to H5P3O10, tripolyphosphoric acid, by the reaction... 

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