Metal phosphorus—hydrogen

Phosphorus—Hydrogen Bond. A hydrogen bound to phosphoms has Httie acidic or hydric character. Most of the reactions the bond undergoes are those of a reducing agent. P—H bonds are formed by hydrolysis of active metal phosphides or phosphoms haUdes, by the rearrangement of P—O—H or P—S—H linkages, or by the hydrolysis of P—P bonds (6,17). 

Pauling, L. (1977) "The nature of bonds formed by the transition metals with hydrogen, carbon, and phosphorus," Acta Crystal-logr., in press. 

Pauling, L. Nature of the Bonds Formed by the Transition Metals with Hydrogen, Carbon, and Phosphorus Acta Crystallogr. 1978, B34, 746-754. 

Because organophosphorus compounds are important in the chemical industry and in biology, many methods have been developed for their synthesis [1]. This chapter reviews the formation of phosphorus-carbon (P-C) bonds by the metal-catalyzed addition of phosphorus-hydrogen (P-H) bonds to unsaturated substrates, such as alkenes, alkynes, aldehydes, and imines. Section 5.2 covers reactions of P(lll) substrates (hydrophosphination), and Section 5.3 describes P(V) chemistry (hydrophosphorylation, hydrophosphinylation, hydrophosphonylation). Scheme 5-1 shows some examples of these catalytic reactions. 

Figure 11 Details of the calculation of the maximum semicone angle, 6/2. The point of contact of the cone-generating vector M - X from the metal, with the van der Waals sphere of the hydrogen atom, is coplanar with the metal, phosphorus and...

Other neutral fragments eliminated in the fragmentation processes of tris-(dimethylamino) phosphine metal carbonyl complexes appear to contain phosphorus-hydrogen bonds, e. g. 

Sulphur dioxide likewise reduces the acid to ehlor-platinous acid, and if added in excess gives rise to complex sulphite derivatives. Yellow phosphorus reduces it to the metal, whilst hydrogen phosphide causes hypophosphites or phosphides to form, according to circumstances. 

After the discovery of ozone, Schonbein s most important chemical contributions were guncotton and collodion (see p. 195) and his work on what was later called autoxidation , on which he published extensively. In autoxidation a substance is oxidised spontaneously by atmospheric oxygen, part of which combines with it, while at the same time another part is converted into ozone or antozone (hydrogen peroxide), or combines with another substance. Ozone is formed by the oxidation of phosphorus, hydrogen peroxide by the oxidation of metals in presence of water, and indigo is oxidised when oxygen combines with turpentine or benzaldehyde. In such reactions, Schdnbein... 

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