Rhodium organometallic compounds

A large number of organometallic compounds are based on transition metals Examples include organic derivatives of iron nickel chromium platinum and rhodium Many important industrial processes are catalyzed by transition metals or their complexes Before we look at these processes a few words about the structures of transition metal complexes are m order... 

R. S. Dickson, Organometallic Chemistry of Rhodium and Iridium, Academic Press, New York, 1983, 432 pp. C. White, Organometallic Compounds of Cobalt, Rhodium and Iridium, Chapman Hall, London 1985, 296 pp. 

The coordination of the alkyne to the rhodium catalyst allows the carborhodation of the triple bond to afford the vinylrhodium intermediate 47 (Scheme 14). The rearrangement of this organometallic compound into the 2-(alkenyl)phenylrhodium intermediate 48 is evidenced by one deuterium incorporation resulting from the deuter-iolysis of the Rh-C bond. The addition of the phenylrhodium intermediate 45 must occur before its hydrolysis with water. The 2-(alkenyl)phenylrhodium intermediate 45, generated by the phenylrhodation of an alkyne followed by... 

Organometallic compounds, 14 550-551 25 71. See also Organometallics carbides contrasted, 4 648 as initiators, 14 256-257 iridium, 19 649-650 molybdenum(III), 17 27 osmium, 19 642-643 palladium, 19 652 platinum, 19 656-657 reaction with carbonyl groups, 10 505-506 rhodium, 19 645-646 ruthenium, 19 639 sodium in manufacture of, 22 777 titanium(IV), 25 105-120 Organometallic fullerene derivatives,... 

The reaction of bis-phenylpropargyl ether (321) with tris(triphenylphosphine)rhodium chloride in benzene or toluene led to the formation of the unusual organometallic compound (322), which can be viewed as a derivative of an oxygen-rhodium pentalene system. Reaction of the rhodium complex (322) with sulfur leads to the corresponding 4,6-diphenyl-l,3-dihydro[3,4-c]furan (323). The selenium and tellurium analogs (324) and (325) were made in a similar manner (Scheme 111) (76LA1448). 

W. D. Jones, and F. J. Feher, Alkane Carbon-Hydrogen Bond Activation by Homogeneous Rhodium(I) Compounds, Organometallics 2, 562-563 (1983). 

However, the rapid pace of rhodium chemistry has not been fully reflected in the review literature. The two extant English language reference works have been well overtaken by events.14,15 There is an invaluable compendium of the early work by Griffith,16 and a new edition of Gmelin s handbook has been published very recently.17 However, apart from these last two books and the ever increasing space devoted to the chemistry of the element in undergraduate texts there has been no systematic attempt to review the chemistry of this element apart from its organometallic compounds, which form the subject of the companion series.18... 

There have been a number of reports of indirect coupling constants to carbon in organometallic compounds (see Tables XXXI and XXXII). Several trends are discernible. For transition metal complexes, the trends in V(i3C—M—3ip) and (i C—M— H) appear to follow those observed for V( P—M— H) and V( P—M— P). For complexes of ruthenium, osmium, rhodium, iridium, palladium, and platinum, it is generally found that V(A—M—B) (A, B = P, H) is large when... 

C. White, Organometallic Compounds of Cobalt, Rhodium, and Iridium , Chapman and Hall, New York, 1985. 

A. Segnitz, Organometallic Compounds of Cobalt, Rhodium, Iridium, Nickel, Palladium, Houben-Weyl Methods of Organic Chemistry , 4th edn., Houben-Weyl, Stuttgart, Fed. Rep. Ger., 1984, Vol. 13, Pt. 9B, p. 1062. 

In some cases, it is possible to couple an alcohol with an organometallic compound. Allylic alcohols are coupled with alkylmagnesium bromides in the presence of Ti(OiPr)4, for example. Allylic alcohols can be coupled with arylboronic acids in ionic liquid solvent and a rhodium catalyst. The palladium-catalyzed... 

Other organometallic compounds, including aUylic stannanes, allylic samarium, allylic germanium, and allylic indium compounds add to aldi-mines in the same manner. Aryltrialkylstannanes also add the aryl group to Al-tosyl imines using a rhodium catalyst and sonication. Catalytic enantioselective addition reactions are well known, including reactions in an ionic liquid.Allylic... 

Reviews have appeared of the photophysics of molybdenum complexes, primary and secondary processes in organometallic chemistry, flash photolysis of Pe(CO)5 and Cr(CO)g, dinuclear manganese carbonyl compounds, the photochemistry of metal complexes isolated in low temperature matrices, cluster complexes, diene complexes, photoproduction of coordinativeiy unsaturated species containing rhodium or iridium, and redox chemiluminescence of organometallic compounds.Synthetic and metal organic photochemistry in industry has also been reviewed. 

Organometallic compounds of rhodium have the metal center in oxidation states ranging from +4 to -3. but the most common oxidation states are +1 and +3. The Rh(I) species have a d electron configuration and both four coordinated square planar and five coordinated trigonal bipyramidal species exist. Oxidative addition reactions to Rh(I) form Rh(III) species with octahedral geometry. The oxidative addition is reversible in many cases, and this makes catalytic transformations of organic compounds possible. Presented here are important reactions of rhodium complexes in catalytic and stoichiometric transformations of organic compounds. 

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