Manganese phosphonate

LB deposition of the TTF-LBl amphiphile from an aqueous Mn+ subphase forms Y-type hlms with stoichiometry Mn2 (11L-LB1 )(H2 0)2. Static x measurements show that the hlms become magnetic near 11.5 K when the manganese phosphonate network orders as a canted antiferromagnet. This is illustrated in Fig. 6.44. 

Nowack, B., and A. T. Stone, Degradation of nitrilotris(methylene-phosphoric acid) and related amino(phosphonate) chelating agents in the presence of manganese and molecular oxygen , Environ. Sci. Technol., 34,4759-4765 (2000). 

Table 8.6 Zinc [Manganese] Polymer Phosphonate [Zinc Organic] Program Selection Notes.

Aluminium, 0048 Ammonium phosphinate, 4549 Barium phosphinate, 0210 f Benzaldehyde, 2727 1,4-Benzenediol, 2326 Bis(hydrazine)tin(II) chloride, 4064 Calcium acetylide, 0582 Calcium phosphinate, 3925 Chromium(II) chloride, 4046 Chromium(II) oxide, 4235 Chromium(II) sulfate, 4238 Copper(I) bromide, 0264 Diacetatotetraaquocobalt, 1774 Diisobutylaluminium hydride, 3076 f 1,2-Dimethylhydrazine, 0951 1,2-Diphenylhydrazine, 3511 Dipotassium phosphinate, 4425 f Ethanedial, 0719 f Formaldehyde, 0415 Formic acid, 0417 Gallium(I) oxide, 4405 Glucose, 2513 f Hydrazine, 4515 Hydroxylamine, 4493 Hydroxylaminium phosphinate, 4550 Hyponitrous acid, 4464 Iron(II) chloride, 4055 Iron(II) hydroxide, 4386 Iron(II) sulfate, 4393 Fead(II) phosphinate, 4526 Fead(II) phosphite, 4530 Fithium dithionite, 4682 Magnesium, 4685 Magnesium phosphinate, 4512 Manganese(II) phosphinate, 4514 f Methylhydrazine, 0500 Phenylhydrazine, 2366 Phosphinic acid, 4498 Phosphonic acid, 4499 Phosphonium iodide, 4510 Potassium, 4640 Potassium hypoborate, 0163... 

Zinc [37], manganese [38], molybdenum [34], and vanadium [40,41] also form lamellar structures. For example, molybdenyl phenylphosphonate forms a linear structure with double chains in which the molybdenyl oxygens of the adjacent chains point toward each other and the phenyl groups are on the outside [42], As is the case with zirconium phosphate and phosphonate, the layered nature of the above metal phosphonates is similar to that of the respective phosphates. Among these, vanadium phosphonates have generated greater interest in view of their importance as industrial catalysts. 

Figure 19.1 Synthetic scheme for example pheromone components. Abbreviations al and a2 = Wittig-Homer condensations with triethyl 2-phosphonopropionate and triethyl 2-phosphonobutyrate, respectively b = reduction of ester with lithium aluminum hydride c = partial oxidation of alcohol with manganese dioxide to aldehyde dl and d2 = Wittig condensations with ethyltriphenylphosphonium bromide and propyltriphenylphosphonium bromide, respectively e = condensation with dimethylhydrazone phosphonate reagent f = hydrolysis under acidic conditions. Compound numbers are as in Table 19.1.

Fig. 19 The low-pH chain structure of manganese /)-(phosphono-methyl)benzoate, with ail carboxylate oxygens and half the phosphonate oxygens protonated.59 Gray spheres denote carbon, red oxygen, white hydrogen, and green phosphorus, with MnOs octahedra in blue. Reproduced with permission. Copyright 2006, Royal Society of Chemistry.

P-Ketoesters are oxidized at the a-position with oxygen in the presence of either manganese(II) acetate " or cobalt(II) chloride." Cyclic allyl phosphonates give y-acetoxy a,p-unsaturated phosphonates when they are exposed to oxygen in HOAc containing PdCl2 and isopentyl nitrite. " Tertiary amine oxides are formed under cooxidation conditions, that is, O2, Fe203, and isovaleraldehyde. "... 

Dimethyl H-phosphonate reacts with calcium dichloride at 70 °C, with manganese acetate at 112 °C, and with calcium nitrate at 115 °C. Kinetic investigations [304] have shown that the reaction takes place as a bimolecular substitution of the second order. There is no difference in the reaction rate of the substitution of both alkyl groups. In general, it decreases with increase in the length of the carbon chain in the alkoxy group. 

Lamellar or linear structures are also formed by various other metal ions, such as zinc, (268) manganese, (269) molybdenum, (270) and vanadium (271,272). Among these other solids, vanadium derivatives attracted significant attention due to their potential as industrial catalysts. The structures of the metal phospho-nates are similar to those of the corresponding phosphates, in a manner similar to the zirconium phosphate/phosphonates. Polymerization of phenylphosphonate, for example, with Mo(IV) resulted in a linear double-stranded structure where the phenyl groups are positioned on the outside of the linear structure (273). These othCT metal derivatives are bound to yield many future investigations regarding the fundamental and applied chemistry of layered mataials. 

Although the structural chemistry of molybdenum and vanadium phosphates is very diverse these compounds seem to be prototypes for open framework transition and main group metal phosphates. Recent results have shown that zeolite-like compounds like zinc/cobalt phosphates [731, indium phosphates [74], nickel/aluminum phosphates [75], cobalt/boron phosphates [76], manganese and cobalt phosphonates with giant 44-membered rings forming ellipsoidal cavities [77] can be synthesized. All these examples show that the diverse chemistry of octahedral-tetrahedral framework structures is a vast field where... 

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