Oxygen four-coordinate

Boric oxide is an excellent Lewis acid. It coordinates even weak bases to form four-coordinate borate species. Reaction with sulfuric acid produces H[B(HSO 4] (18). At high (>1000° C) temperatures molten boric oxide dissolves most metal oxides and is thus very corrosive to metals in the presence of oxygen. 

Bidentate sulphoxides, such as 1,3-bis(methylsulphinyl)propane, 1,4-bis(methyl-sulphinyl)butane and 1,2-bis(ethylsulphinyl)ethane, have been synthesized and employed as ligands toward Mn2 +, Co2 +, Ni2 +, Cu2 + and Zn2 + 204. All metal ions are bound to the ligands via the oxygen of the sulphoxide groups and are six-coordinate, as shown in Scheme 20, with the exception of Cu2+, which is four-coordinate. 

The framework of the structure consists of silicon tetrahedra (four oxygen ions coordinated about a silicon ion at the comers of an approximately regular tetrahedron) and aluminium octahedra and (or) tetrahedra, with Si-0 = 1.59 A, Al-0 = 1.89 A in octahedra, 1.75 A in tetrahedra, as observed in other aluminosilicate crystals. 

The divalent Co(salen) complex (69a) is one of the most versatile and well-studied Co coordination compounds. It has a long and well-documented history and we shall not restate this here. Recent applications of (69a) as both a synthetic oxygen carrier and as a catalyst for organic transformations are described in Sections 6.1.3.1.2 and 6.1.4.1 respectively. Isotropic shifts in the HNMR spectrum of low-spin Co(salphn) (69b) were investigated in deuterated chloroform, DMF, DMSO, and pyridine.319 Solvent-dependent isotropic shifts indicate that the single unpaired electron, delocalized over the tetradentate 7r-electron system in CHCI3, is an intrinsic property of the planar four-coordinate complex. The high-spin/low-spin equilibrium of the... 

Fig. 10. Chemical structures of some oxygen carriers (A) five-coordinate cobalt Schiff-base Co(salPr), (B) four-coordinate cobalt Schiff-base Co(3-MeOsaltmen), (C) cobalt dry-cave.

Figure 8.26 The four-coordinated oxygen atom in basic beryllium acetate OBe4(CH3C02)6- Three of the acetate groups are shown as curved lines.

The results presented in Section IV.D.l show that the net loss of the dioxorhenium(VII) species, and the ultimate formation of the phosphate R3PO, must occur in two stages because the rate of reaction (17) shows a direct first-order phosphine dependence. That said, the chemical mechanism is still open to discussion does the first step entail abstraction of an oxo oxygen or addition to it If the former, the cycle is completed by PR3 coordination to a four-coordinate rhenium intermediate if the latter, the addition step is then followed by yet another ligand substitution reaction. The alternatives are presented in Schemes 1 and 2. 

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