Amine oxides arsines

Considerable controversy surrounds the nature of the bonding in amine oxides and analogous phosphine and arsine oxides. These species are often depicted in textbooks as double-bonded (0=PH3, 0=AsH3) in order to rationalize the unusually short bond lengths. However, both theoretical wavefunction analysis53 and NMR... 

A facile method for the preparation of a variety of stabilized arsonium ylides in good yield has been developed by the action of active methylene compounds with tertiary arsine oxide or tertiary arsine dihalide. Thus triphenyl-arsine dihalides react with a number of active methylene compounds in the presence of a tertiary amine to afford arsonium ylides (6) (40). The reaction of triphenylarsine oxide with active methylene compounds in the presence of either acetic anhydride or triethylamine-phos-phorus pentoxide gave rise to arsonium ylides (6) (32, 36. 65, 67). 

Oxo-rhenium complexes can catalyze various OAT reactions between suitable oxo-donors (XO = sulfoxides (R2SO) tertiary amine A-oxides (R3NO) pyridine A-oxide (C5H5NO, PyO) triphenyl-phosphine, -arsine, or -stilbene oxide (R3AO) (A = P, As, Sb) peroxides (Bn OOH, H2O2) ... 

Amine N-oxides, phosphine oxides, arsine oxides, and related ligands. The prototypical system for extraction of the uranyl ion from aqueous solution into organic solvent is tributylphosphate in hydrocarbons such as kerosene. This has stimulated interest in understanding the coordination chemistry of actinyl ions with P=0 (and related) functional groups in order to optimize extraction efficiency or discrimination among actinides to be separated. Of all classes of neutral group 16-atom donor ligands, phosphine oxide adducts are the most common examples of complexes of transuranic elements (Np, Pu). 

CCC (1987) contains a section on sulfoxides, amide, amine oxides, and related ligands that have sections on phosphine oxides and arsine oxides.159 Phosphine and arsine oxide complexes of yttrium and the lanthanides were highlighted in CCC (1987).1 Scandium and yttrium phosphine oxide complexes have been reinvestigated and characterized by multinuclear NMR and X-ray... 

The reaction of arsines with chloramine-T and related compounds gives rise to arsinimines (86,300) though these are usually isolated as the hydroxy sulfonamides (300,301,302). The hydrated compounds can also be prepared from the tertiary arsine oxide, or dihydroxide, and the appropriate amine. 

Conversion of aliphatic and aromatic amine N-oxides to corresponding amines, phosphine oxides to phosphines and triaryl arsine oxides to triaryl arsines have also been achieved. These reactions require the presence of HMPA as cosolvent (Zhang and Lin, 1987). 

Sulfonyls RR S02 Sulfinyls RR SO Seleninyls RR SeO Phosphoryls RR R TO Arsine oxides RR R"AsO Amine oxides RR R"NO Nitrosos R—N=0 Nitros RNO2 Isocyanates R—N=C=0... 

Table 4.22 - Oxygen bases oxides of organoderivatives of elements of group 15 phosphoryl bases, amine A -oxides, arsine oxides [94, 96].

Gold(I) complexes of the type [AuCl(PPh3)ra] (n= 1, 2) or [Au(N03)(PPh3)] show an excellent performance towards oxidative addition carbonylation or aromatic amines to form corresponding carbamates, and also towards the carbonilation of aliphatic amines to produce either alkylureas or formamides.2552,2553 Cationic gold(I) compounds of the type [AuL]+ where L = phosphine, phosphite, or arsine are excellent catalysts for the addition of alcohols to alkynes.2554... 

However, with soft electron pair acceptors such as Pt2+, Ag+, and Ir+, phosphines are stronger Lewis bases than are NH3 and amines, so phosphines and arsines interact better with class B metals than do amines. Generally, phosphines and arsines form stable complexes with second- and third-row transition metals in low oxidation states. 

Oxidations of Amines, Amides, Ethers, Sulfides, Phosphines, Arsines, Stibines and Miscellaneous Substrates... 

Abstract This chapter principally concerns oxidations of organic substrates containing N, O, S, P, As and Sb. Oxidations of amines are covered first, including primary amines to nitriles or amides secondary amines to imines or other products tertiary amines to N-oxides or other prodncts (Section 5.1) and the oxidation of amides (5.2). Oxidation of ethers to esters or lactones follows (5.3), then of sulfides to sulfoxides or sulfones (5.4) and of phosphines, arsine and stibines to their oxides (5.5). A final section (5.6) concerns such miscellaneous oxidations not covered by other sections in the book. 

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