Arsine syntheses with

During the decade 1996-2005, in this category of heterocycles, the major interest has been the synthesis and reactions of benzarsepins, arsocanes, and cyclic esters of arsenic(m) acids. In contrast, little work has been done in the area of arsine heteromacrocycles with two or more arsenic atoms. Readers are referred to the corresponding sections of CHEC-II(1996) <1996CHEC-II(9)971 > for information concerning earlier works on macrocyclic polyftertiary arsines) and related compounds. 

The first synthesis of an optically active tertiary arsine sulphide from an optically active tertiary arsine was reported in 1962 , compounds 157 and 158 being prepared by heating the respective optically active tertiary arsines with sulphur in benzene. Along similar lines, arsine sulphides 136,159-164 were prepared and isolated (Table 8). The sulphurization of the tertiary arsines occurs with retention of configuration at arsenic. 

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). 

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 ... 

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...

The earliest examples of higher oxidation states of nickel were given in 19133021 and the first nickel(III) complex, Ni(PEt3)2Br3, was isolated by Jensen in 1936. 2 In 1907 Hall reported the occurrence of nickel(IV) in a heteropolymolybdate,3023 and in 1951 Nyholm described the synthesis of a nickel(IV) complex with the chelating arsine o -phenylenebisdimethylarsine (diars).3024 In the last 15 years the chemistry of nickel(III) and nickel(IV) complexes has largely developed due to the use of electrochemical methods of synthesis. 

Cationic methylplatinum(II)-nitrile complexes of the type m is-PtMeL2(NCR)+X have been isolated by the reaction of //vms-PtMeClL2, where L = dimethylphenylphosphine or trimethyl-arsine, with an aryl nitrile and AgX, where X = BF4, PF. Use of pentafluorobenzonitrile and 2,3,5,6-tetrafluorotetraphthalonitrile in alcohol has led to the synthesis of a series of imino ether complexes. A mechanism for imino ether formation, involving nucleophilic attack by an alcohol at a coordinated nitrile, is suggested and the course of the reaction is shown to be dependent not only on the alcohol but also on the size of the anion used.110... 

The synthesis of the first arsabenzene, 9-arsaanthracene, 6, was simultaneously communicated by Bickelhaupt16) and Jutzi17> in 1969. The elimination of hydrogen chloride from 9,10-dihydroaarsanthracene 7 afforded 6. These precursors are available from either reduction of the corresponding arsinic acids 816,18) or by the exchange reaction of dihydrostannaanthracenes 9 with arsenic trihalides 17). 

Arsinic adds are obtained also as by-products in the Bechamp synthesis. For example, 4,4 -diaminodiphenylarsinic add, along with a... 

When treated with arsine, Cp Mn(CO)2(THF) gives [Cp Mn(CO)2]2 AsH, which converts into [/a-(Cp )Mn(CO)2]2As2 with elimination of H2 246,247 xhiS contrasts with the reaction of the analogous nonsubstituted cyclopentadienyl complex, which under similar circumstances yields [CpMn(CO)2]4As2.246,247 To achieve selectivity in the synthesis of the sensi-... 

A still better synthesis for such spiroarsoranes was finally found in the reaction of the bis-2,2 -biphenylylenearsonium ion 120 (5,5 -spirobi[5f7-dibenzarsolium]) with a variety of organyllithium or Grignard reagents 121 123>, 120 being readily accessible from appropriate chlorinated arsine precursors 119a, b 121). 

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