Metaphosphates, determination structure

As cyclophosphates and the catenaphosphate anion (together termed metaphosphates) share the basic composition (PO3 ) , crystal-structure analysis is often the only way to determine which species is present, although IR spectroscopy may be useful (see Section 3.2.1). Different isomers of the same metaphosphate composition are often found. Six crystal forms (A-F) of M(P03)3 (M = Al, Cr, Mn, Fe, Ga) have been identified, three of which have been structurally characterized and found to contain cyclotetraphosphate (form A), cyclohexaphosphate (B), and catenaphosphate (C) anions. 

Further progress has been reported in the chemistry of CT X, -p -bonded systems. Full details of such systems stabilised by intramolecular coordination, as in, e.g., 334, have been described. The kinetically stable system 335 has been prepared and its solid state structure determined . The P-halobis(imino)-CT -phosphoranes 336 have also been prepared, and detailed NMR studies of bis(imino) phosphoranes reported . Quin s group has continued studies of the generation and characterisation of reactive a X -systems, e.g., 337 ". Methods for the generation of monomeric metaphosphate esters in solution have been investigated. A theoretical approach has been used to probe the mechanism of the reaction between phosphanylnitrenes 338 and boranes. The thiophosphonic anhydride 339 behaves as a source of the dithioxophosphorane... 

In physical and theoretical methods there has been a notable increase in the use of recently developed techniques - most of which have trendy acronyms. Thus DRAMA P NMR has been used to determine internuclear P-P distance in a phosphine sulfide 4,8-residue substituted decapeptide, and XANES has been applied to structural studies of phosphine selenides. In the mass spectral field MALDI-TOF has been found to be better than FAB for the determination of the mass spectra of nucleotide triphosphates, LA-FTICR has been used to study tris(cyanoethyl)phosphine and metaphosphates have been detected for the first time by laser photoionisation MS. ERMS was shown to be a powerful technique for the analysis of structurally similar organophosphate insecticides (OPs) and trace quantities of OPs can be determined by Cl using water as the ionising agent. 

Structure of the substrate and the reaction conditions determine the transition state for reaction with a particular nucleophile 104, 105). The extreme cases are generally described as the dissociative and associative substitution mechanisms. The fully dissociative mechanism entails the formation of monomeric metaphosphate monoanion as a discrete intermediate and was first formulated by F. H. Westheimer, who pioneered the physical organic chemistry of the hydrolysis of phosphate esters 106, 107). This mechanism is depicted in Eq. (40) and is possible only for phosphomonoesters with good leaving groups, examples of which are shown. 

Thurn and Krebs Clearfield and Smith Niemeyer and Richter Crystal structure of Hittorf s Violet phosphorus determined Layer structure of a-Zr(HP04>2.H20 estabhshed Cyclic metaphosphates first detected in hving matter... 

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