Decarboxylation syntheses of transition metal organometallics,II.trans-carbonyl(polyhalogenophenyl)bis(triphenylphosphine)rhodium(I) compounds |
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| Authors: | Glen B. Deacon Suellen J. Faulks Jack M. Miller |
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| Affiliation: | (1) Department of Chemistry, Monash University, 3168 Clayton, Victoria, Australia;(2) Department of Chemistry, Brock University, St. Catharines, L2S 3A1 Ontario, Canada |
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| Abstract: | Summary The rhodium(I) carboxylates,trans-RhO2CR(CO)(PPh3)2 (R = C6F5, C6Cl5,p-HC6F4,m-HC6F4,o-HC6F4,p-McOC6F4, 4,5-H2C6F3, 3,5-H2C6F3, or 2,6-F2C6H3, have been prepared by reaction of RhH(CO)(PPh3)3 with the appropriate polyhalogenobenzoic acids in ethanol and/or by reaction oftrans-RhCl(CO)(PPh3)2 with the appropriate thallous carboxylates in benzene. Decarboxylations with formation of polyhalogenoarylrhodium(I) compounds,trans-RhR(CO)(PPh3)2 (R = C6F5, C6Cl5,p-HC6F4,m-HC6F4,p-MeOC6F4, 4,5-H2C6F3 or 3,5-H2C6F3), have been achieved either by decomposition of the corresponding rhodium(I) carboxylates in pyridine or by reaction oftrans-RhCl(CO)(PPh3)2 and the thallous carboxylates in pyridine, but the derivatives R =o-HC6F4 or 2,6-F2C6H3 could not be obtained by this method. The rate of decarboxylation decreased in the sequence R = C6F5 >p-MeOC6F4 >p-HC6F4 >m-HC6F4 > 4,5-H2C6F3 > 3,5-H2C6F3.Part 1, ref. 10.Preliminary communication, ref. 9. |
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