Arsines synthesis

Henderson W, Alley SR (2002) User-friendly primary phosphines and an arsine synthesis and characterization of new air-stable ligands incorporating the ferrocenyl group. J Organomet Chem 656 120-128... 

A. Preparation.—The first reverse Wittig olefin synthesis has been reported. Triphenylphosphine oxide and dicyanoacetylene at 160 °C gave the stable ylide (1 78%) the reaction was reversed at 300 °C. No comparable reaction was observed with a variety of other activated acetylenes but tri phenyl arsine oxide gave the corresponding stable arsoranes with dicyanoacetylene (— 70 °C), methyl propiolate, hexafluorobut-2-yne, dimethyl acetylene dicarboxylate, and ethyl phenylpropiolate (130 °C). 

Detailed procedures for the synthesis of various often used [Ni°L4] complexes (L = phosphines, arsines, stibines, alkyl isocyanides) and [Ni°L 2] complexes (L = bipyridine, phenantroline, diphosphines, diarsines) have been compiled.2413... 

The number of gold complexes containing tertiary phosphines, arsines, or stibines as ligands is large because of the wide use of the fragment AuL+, mainly with L = PPh3, in the synthesis of... 

The synthesis of alkali metal organophosphides and arsenides is usually most conveniently achieved by the direct metalation of a primary or secondary phosphine/arsine with a strong deprotonating agent such as an alkyllithium or an alkali metal hydride ... 

Several methods are available for the synthesis of cycloarsoxanes (a) hydrolysis of organoarsenic(III) dihalides RASX2 (X = Cl, Br, I), (b) reduction of arsonic acids RAsO(OH)2 and (c) oxidation of primary arsines RASH2 or cyclopolyarsines (RAs) . The tetramer cyclo-(MeAsO)4 exhibits the boat-chair conformation, whereas the mesityl derivative cyclo-(MesAsO)4 adopts the crown conformation (Figure 11.24). The As-O bond distances are in the range 1.77-1.82 A, typical for single bonds. 

A simUar phosphamethin-cyanine synthesis starting from tris-trimethylsilyl-phosphine has been described by Markl. Using this procedure, arsamethin-cyanines can also be prepared from tris-trimethylsilyl-arsin... 

This section is divided into two main subsections. The first describes the synthesis and characterization of phosphine-stabilized gold clusters. The second focuses on the synthesis and characterization of thiol-stabilized gold clusters and the study of other stabilizers such as arsines or boranes are described. 

Although most of the structurally characterized gold clusters are phosphine-based systems, in recent years some studies have focused on the synthesis of gold clusters with other stabilizers coexisting with phosphines such as thiols, arsines and boranes. Certain heteroleptic gold clusters stabilized with these ligands and arylphosphines in the same molecule have been structurally characterized. 

Trimethylarsonioribosides have also been synthesized (Fig. 5). Compound 33 was first isolated from a brown alga and was subsequently prepared by addition of methyl iodide to the arsine obtained on reduction of the natural product 17 with borohydride solution (64). Compound 33 has also been prepared by using 2,3-dimercapto-propanol as the reductant, and this procedure was similarly used for the synthesis of compounds 34 to 37 from the respective dimethylated compounds (65). 

Table 3 Summary of Nickel Complexes with Phosphines, Arsines and Stibines, and their Methods of Synthesis...

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