Arsines substitution

Whyman, R., Polynuclear phosphine- and arsine-substituted rhodium carbonyls, preparation of Rh4(CO)iiL (L=PPhs, AsPha, P(p-MeCeH4)3 P(p-FC6H4)s) and Rh4(CO)io(diphos), Chem. Comrnun. p. 230 (1970). 

However, when the substrate ArX has a low-energy LUMO, such as 4-chlorobenzophenone [58], 2-chloroquinoline [58], and 6-chloro-2,4-dimethoxypyrimidine [60], the extra electron in the radical anion (ArAsPh ) " intermediates is properly stabilized. In these case, the gap between x MO and the a MO of the C—As bonds is large enough, and the transfer of the odd electron to the a MO is unfavorable. As consequence, the C—As bond fragmentation does not occur, and the straightforward arsine substitution products ArAsPh are obtained in 100, 76, and 70% yields, respectively. On the... 

Where X is Br or Q, the free acids may be obtained by acidification of the alkaline solution, but where X is I, the acids must be isolated as salts to avoid reduction of the arsonic acids by HI. Rather than using alkyl haUdes, alkyl or dialkyl sulfates or alkyl arenesulfonates can be used. Primary alkyl haUdes react rapidly and smoothly, secondary haUdes react only slowly, whereas tertiary haUdes do not give arsonic acids. AHyl haUdes undergo the Meyer reaction, but vinyl hahdes do not. Substituted alkyl haUdes can be used eg, ethylene chlorohydrin gives 2-hydroxyethylarsonic acid [65423-87-2], C2H2ASO4. Arsinic acids, R2AsO(OH), are also readily prepared by substituting an alkaU metal arsonite, RAs(OM)2, for sodium arsenite ... 

A number of substituted phenylarsonic acids have been prepared by means of the Bart reaction (121). For the preparation of arsinic acids a sodium arylarsonite is used, and mixed diaryl or alkylarylarsinic acids can be prepared ... 

Arsine (ASH3) and phosphine (PH3) are extremely toxic, so less hazardous substitutes such as tertiary butyl arsine, C4H1 j As, and tertiary butyl phosphine, C4H11P, are being considered. 

Complexity in the manganese and rhenium pentarbonyl halides substitution arises from the fact that these decompose in inert solvents to form the halogen-bridged dimers [M(CO)4X]2. Both monomers and dimers react with phosphines, arsines, pyridine, aniline etc. to give the disubstituted compounds M(CO)3XL2. Thus three final products or any mixture of them may be obtained, depending upon the precise reaction conditions... 

The chemistry of these compounds has not been investigated in detail. Scheme 12 summarizes some of the chemistry that has been established for the ruthenium complex RugClCO) (192). In general, the octahedral metal-carbido skeleton is maintained, substitution reactions occurring with phosphine, phosphites, and arsine ligands. Base attack leads to the production of the anion [Ru8C(CO)16P, which is... 

This type of reaction was originally carried out with ethyl iodide1 and has been extended to other alkyl halides,2 halogeno-carboxylic esters3 and to substituted arsine halides.4 Incidentally when p-toluene sulphonyl chloride and naphthalene-2-sulphonyl chloride were allowed to react with sodium diethyl phosphite, the corresponding disulphones were obtained in small yield.5... 

Rhenium(0) compounds are rare and frequently lie in the realm of the organometallic chemistry. A simple example is decacarbonyldirhenium(0) in which two staggered, square-pyramidal Re(CO)5 fragments are held together by a single rhenium-rhenium bond. Substitution of carbonyl ligands is possible by tertiary phosphines and arsines, silanes and isocyanides, and binuclear Re-Re, Mn-Re, and Co-Re complexes have been studied. " Successive replacement of CO ligands can readily be observed by vibrational spectroscopy. This has been demonstrated... 

Aromatic substitution by the SrnI reaction, 54, 1 Arsinic acids, 2, 10 Arsonic acids, 2, 10... 

The complex reacts readily with ligands such as tertiary phosphines, phosphites, or arsines to give substitution of a CO ligand on the cobalt atom. With CO, however, the complex reacts to give 2-phenylindazolone and 3-phenyl-2,4 lif, 3f/)-quinazolinedione,15 whereas the reaction with CO and hexafluoro-2-butyne affords an anilinoquinoline, probably via an intermediate complex in which the alkyne and CO have inserted into the Co—C bond.16... 

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