Crystalline nanoporous materials like zeolites and metal phosphates (e.g. AlPOs) are used commercially for catalysis, adsorption, molecular sieving, and ion exchange. Their properties are related to both their porous architectures and chemical compositions. Materials that incorporate tin(II) and antimony(III), with stereochemically active lone electron pairs, could impart properties different from those of materials based on aluminum, cobalt, zinc, iron, and other metals that adopt [MO4] tetrahedra. Exploratory hydrothermal synthesis resulted in thirty new tin(II) and antimony(III) materials, including the first open-framework antimony(III) phosphate. Structure determination was by single crystal X-ray diffraction. Some materials incorporate a three-ring chain motif observed in other metal phosphates. Previously proposed metal phosphate formation mechanisms are shown not to adequately describe its formation. A new mechanism is proposed, adapting the Partial Charge Model of Livage, et al. to tin(II) and antimony(III) phosphates. This mechanism, starting from open chain metal phosphate 'wires' (with M-O-P bonds), is then extended to other metal phosphates.

This book presents the synthesis, properties, uses, structure, and safety of iron (III) phosphate, as well as its use as an intercalation electrode in lithium-ion batteries, despite having low electronic conductivity. In the synthesis of organic compounds, iron (III) phosphate catalyzes the one-pot synthesis of dihydropyrimidinones and thiones, and 2, 4, 5triarylated imidazoles. It also results in the acetylation of alcohols and phenols, the tetrahydropyranylation and tetrahydrofuranylation of alcohols and phenols, as well as the synthesis of polyhydroquinoline derivatives, 2-substituted benzimidazoles, 1, 2-disubstituted benzimidazoles, 1,2,4,5-tetra-arylated imidazoles, and bis(indolyl)methanes. Furthermore, it catalyzes the one pot three-component mannich reaction, 2-substituted imidazolines, ß-amido carbonyl compounds, 1,4-dihydropyridines, 4,4-diaminotriaryl methanes-leucomalachite materials, N-substituted pyrroles, 7,10,11,12-tetrahydrobenzo[c] acridin-8(9h)-ones, and 4,6-disubstituted 2-aminopyridine-3-carbonitriles. It results in the one-pot synthesis of octahydroquinazolinones, the conversion of tetrahydropyranyl ethers to acetates, dihydropyrimidinones, thiones, as well as β-amino ketones. In the authors opinion, this book could be beneficial for researchers, graduates, and post graduate students, as well as for professionals in the chemical and medicinal industries in the preparation of raw materials using green methods.

Chapter 1 takes the format of an "Outlook", and sets forth the case for developing sustainable methods in the synthesis of phosphorus-containing compounds. Methods used by nature for phosphorus-carbon bond-formation, or in the chemistry of other elements such as silicon, are discussed as model processes for the future of phosphorus in chemical synthesis. Chapter 2 describes the discovery of [TBA][P(SiCl3)2], prepared from [TBA]3[P3O9]-.2H2O and trichlorosilane. The bis(trichlorosilyl)phosphide anion is used to prepare compounds that contain P–C, P–O, P–F, and P–H bonds in a method that bypasses white phosphorus (P4), the traditional route to organophosphorus compounds. Chapter 3 extends the phosphate precursors to [TBA][P(SiCl3)2] from trimetaphosphate to crystalline phosphoric acid. Balanced equations are developed for the formation of [TBA][P(SiCl3)2] from phosphate sources and the byproducts are identified as hexachlorodisiloxane and hydrogen gas. Extension of trichlorosilane reduction to bisulfate provides improved access the known trichlorosilylsulfide anion, [TBA][SSiCl3]. This anion was used as a thionation reagent to prepare thiobenzophenone and benzyl mercaptan from benzophenone and benzyl bromide, respectively. Chapter 4 describes the synthesis of neutral phosphine, HP(SiCl3)2, obtained by protonation of [TBA]1 with triflic acid. HP(SiCl3)2 is a highly efficient reagent for photochemical hydrophosphination of terminal alkenes. The phosphorus-silicon bonds in the hydrophosphination products can be functionalized to provide compounds of the general formulae: RPCl2, RPH2, [RP(R')3]Cl, RP(O)(H)(OH), and RP(O)(OH)2. Chapter 5 describes a method to prepare phosphiranes (three-membered rings that contain a phosphorus atom) from anthracene-based phosphinidene precursors and styrenic olefins. The phosphinidene transfer reaction requires an organoiron and fluoride catalyst. The resulting phosphirane is prepared in good yield (73%) with high stereoselectivity (>99%). Experimental investigations into the mechanism point toward the intermediacy of an iron-coordinated fluorophosphide species.