Boron-phosphorus complexes

Some defect spectroscopy measurements in n-type a-Si H have been interpreted in terms of close P D pairs (Kocka 1987) and there is also evidence of boron-phosphorus complexes in compensated a-Si H (Boyce et al. 1987). The driving force for pairing is the Coulomb interaction between oppositely charged states. Such a paired state must be treated as a distinct species in the defect reaction, which takes the form,... 

Fluondes of boron, phosphorus, and antimony react with hydrogen fluoride, producing complex fluoroboric, fluorophosphoric, and fluoroantimonic acid,... 

The chemistry of boron-phosphorus compouuds has been reviewed. Numerous boron-phosphorus derivatives have been reported, but relatively few boron-arsenic or boron-antimony compounds have been described. Boron-phosphorus compounds are similar in many ways to boron nitrogen derivatives, but the teudeucy to share boudiug electrons in covalent tetrahedral compounds is much more evident with phosphorus thau with uitrogeu. lu fact, most boron phosphorus chemistry iuvolves tetrahedral borou. They are typically either phosphiue-boraue complexes, such as R3P BR j, or phosphinoboranes (R2PBR2) , cyclic or polymeric derivatives of the hypothetical H3P BH3. The chemistry of these compounds and that of boron phosphate and thiophosphate is described below. Boron phosphides are discussed in Section 2.6. 

Silicon s most familiar use is in the production of microprocessor chips. Computer microprocessor chips are made from thin slices, or wafers, of a pure silicon crystal. The wafers are doped with elements such as boron, phosphorus, and arsenic to confer semiconducting properties on the silicon. A photographic process places patterns for several chips onto one wafer. Gaseous compounds of metals are allowed to diffuse into the open spots in the pattern, and then the pattern is removed. This process is repeated several times to build up complex microdevices on the surface of the wafer. When the wafer is finished and tested, it is cut into individual chips. 

Many phosphine-borane complexes Y3P BZ3 have been characterized. They include compounds where Y = alkoxy, alkyl, amino, halide, and hydride groups, and Z = alkyl, halide, and hydride. The stabilities of these complexes vary widely depending on the Lewis acidity and basicity of the boron and phosphorus moieties, respectively. The relative stabilities of Lewis acid-base complexes with BH3 are R3P > R3N > RgAs > R3Sb, but with BF3 the order is R3N > R3P > RsAs > R3Sb. The stabilities of the boron halide complexes of phosphines follow the same order as the amine complexes BI3 > BBt3 > BCI3 > BF3. 

See also Phosphorus(V) chloride-boron chloride complex, synthesis 24 Phosphorus(V) chloride-gallium(III) chloride complex, synthesis 25... 

The phosphorus (V) chloride-boron chloride complex has been prepared by the chlorination of the phosphorus(III) bromide-boron bromide complex at room temperature, by chlorinating an equimolar mixture of phosphorus (III)... 

Phosphorus(V) chloride-gallium(III) chloride is a moisture-sensitive white crystalline solid melting at 368 to 371°. It is insoluble in carbon tetrachloride and chloroform, reacts with acetone, and is immediately hydrolyzed by water. In comparison with the corresponding phosphorus (V) chloride-boron chloride complex, it is much more difficult to sublime. Indications are that the structure is ionic, [PCl4]+[GaCl4]-. 

Barium iodate 1-hydrate, synthesis 4 Indium(I) bromide, synthesis 6 Hexachlorodisiloxane, synthesis 7 Trichlorosilanethiol, synthesis 8 Tris(acetylacetonato)silicon chloride, synthesis 9 Titanium(III)chloride, synthesis 11 Bis[tris(acetylacetonato)titanium(IV)] hexachloro-titanate(IV), synthesis 12 Zirconium(IV) iodide, synthesis 13 (Triphenyl) aminophosphonium chloride, synthesis 19 (Dimethylamido)phosphoryl dichloride, synthesis 20 Bis(dimethylamido)phosphoryl chloride, synthesis 21 Trimeric and tetrameric phosphonitrilic bromides, synthesis 23 Phosphorus(V) chloride-boron trichloride complex, synthesis 24... 

Boron and phosphorus complexes of meso-aryl expanded porphyrins 13H(87)31. 

Phosphorus pentachloride reacts with the methylamine-boron trifluoride complex to give a zwitterionic complex of the type RgP -NR -Y (7.111). 

N2C])H24, 1,2-Ethanediamine, N,N-bis-(1-phenyiethyl)-, S,S) platinum complex, 21 87 N2C2i)H2g, 1,2-Ethanediamine, N,Af -dimethyl-/V, -bis(l-phenylethyl)-, (/ ,/ )-, platinum complex, 21 87 NjOgCgHio, 1,2-Cyclohexanedione, dioxime boron-iron complex, 21 112 N2O2P2C34H30, Phosphorus 1-H), n-nitrido-bis(triphenyl-, nitrite, 22 164 N20 P2Ru3C4 H3o, Ruthenate(l-), decacar-bonyl-p.-nitrosyl-tri-, p,-nitrido-bis(triphenylphosphorus) (1 +), 22 163, 165... 

There have been several reports of coupling between phosphorus and boron in complexes of the type R R2R3P-"BH2 [163-166]. This coupling is believed to be positive and ranges from 13 to 97 Hz as a function of the substituents on phosphorus. As might be expected substitution of halogen for proton on boron markedly increases this coupling. J(B,P) values for Me PBX, X = H, F, Cl, Br are 64, 174,... 

Since many inorganic compounds and complexes contain groups or atoms dealt with previously, the earlier chapters of this book should also be studied for any relevant information. For example, the chapters on silicon, boron, phosphorus and polymers contain a great deal of information relevant to inorganic compounds. Also, if interest is in, say, metal-olefin compounds, then sections dealing with alkenes should be examined, not only because the band positions of the free ligand should be known but also because some bands for these complexes may also be included in these sections. 

Organometallic Complexes of Boron, Silicon, and Phosphorus Analogues of Azoles... 

The first chapter covers organometallic complexes of boron, silicon, and phosphorus analogs of azoles. This chapter continues the series by A. P. Sadimenko (Fort Hare, South Africa) in which he is treating comprehensively organometallic complexes of heterocyclic compounds. So far, he has covered, in the volumes of AHC indicated, complexes of the following heterocycles ... 

N.m.r. studies are reported on the triethylphosphine and trisdi-methylaminophosphine complexes with boron halides, and triethylphos-phine complexes with aluminium chloride. A correlation of Sp with the number of phosphorus ligands in metal carbonyl complexes has led to a qualitative rationalization of 8p in terms of a- and 7r-bonding. ... 

The methods available for synthesis have advanced dramatically in the past half-century. Improvements have been made in selectivity of conditions, versatility of transformations, stereochemical control, and the efficiency of synthetic processes. The range of available reagents has expanded. Many reactions involve compounds of boron, silicon, sulfur, selenium, phosphorus, and tin. Catalysis, particularly by transition metal complexes, has also become a key part of organic synthesis. The mechanisms of catalytic reactions are characterized by catalytic cycles and require an understanding not only of the ultimate bond-forming and bond-breaking steps, but also of the mechanism for regeneration of the active catalytic species and the effect of products, by-products, and other reaction components in the catalytic cycle. 

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