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The rhodium(I) carboxylates, trans-RhO2CR(CO)(PPh~)2 (R = C6F5, C6C1~, p-HC6F~, rn-HC6F4, o-HC6F4, p-MeOC~F4, 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 of trans-RhCI(CO)(PPh3)2 with the appropriate thallous carboxylates in benzene. Decarboxylations with formation of polyhalogenoarylrhodium(I) compounds, trans-RhR(CO)(PPh3)2 (R = C6F5, C6C15, 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 of trans-RhCl(CO)(PPh3)2 and the thallous carboxylates in pyridine, but the derivatives R = o-HC6F4 or 2,6-F2C6H 3 could not be obtained by this method. The rate of decarboxylation decreased in the sequence R =

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317Summary Decarboxylation of metal carboxylates provides a route to numerous main group element organometallics (l' 2) and to several transition metal organometallics in which the central metal has a closed shell (d ~°) configuration O' 21, e.g. organocopper(l) derivatives 13-51. Extensions to compounds with non-d 1° central metals are restricted to some organonickel(ll) derivatives 161. In addition, Tr-allylplatinum(II) complexes have been prepared by decarboxylation of allyloxycarbonyl-II (7) and N-allylcarbamoylplatinum( ) compounds , but the reactants are not carboxylato complexes since the -C(O)O groups are carbon-bonded to platinum. We now report decarboxylation syntheses of some organorhodium(1) and organoplatinum(ll) compounds from suitable metal carboxylates.Reaction of trans-RhCl(CO)(Ph3P)2 with some thallous polyfluorobenzoates, TIO2CR, in pyridine at room temperature (R = CoFs ) or on heating (R = C6F 5 , p-HC6F4 or m-HC6F 4 ) resulted in decarboxylation and formation of the corresponding organorhodium compound (Table).Evidence has been obtained that (1) proceeds by formation (2) and decarboxylation (3) of intermediate carboxylatorhodium(1) complexes. trans-RhCl(CO)(Ph3P) 2 + TIO2CRThus, the trans-RhO2CR(CO)(Ph3P)2 complexes (R = C6Fs (8), C6CIs or p-HC6Fa), obtained by the known (8) reaction of Rhlt(CO)(Ph3P)3 with carboxylic acids, underwent decarboxylation (3) in pyridine at room temperature (R = C6Fs) or under reflux (R = C6C1 s or p-HC6Fa) (Table), and the intermediate carboxylate trans-RhOzCC6F4H-p-(CO)(Ph3P)2 was isolated from treatment of trans-RhCl(CO)(Ph3P): with TIO2CC6F41t-p Decarboxylation-based syntheses of some organorhodium and organoplatinum compounds

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