Preparative use of electrode catalyzed substitution reactions; synthesis of Fe(CO)(PPh3)(η5-C5H5)COCH3

An electrochemical study of the substitution and decomposition reactions of (arene)tricarbonylchromium radical cations

“…This CV is almost identical with the one previously reported18 for (C6Me6)W(CO)3 in MeCN/0.1 M TEAP, and accordingly it seems reasonable to assume that similar chemistry obtains. We found that bulk electrolysis of 6 in MeCN with a platinum basket working electrode gave results difficult to reproduce. Sometimes the number of electrons, n, was close to 2; other experiments gave values between = 1 and 2.…”

A comparison of the energies of double bonds of second-row elements with carbon and silicon

“…The present state of affairs emphasizes the desirability of ascertaining the energies of double bonds involving second-row elements, particularly in comparison with their first-row counterparts. A survey of conventional double bond systems involving carbon (H2C=XH", where XH" = BH, CH2, NH, O, A1H, SiH2, PH, and S) as well as the silicon counterparts, H2Si=XHm with the same XH" groups is the subject of this paper.5, 6 Our results reveal unrecognized aspects of this problem.…”

“…Interestingly, catalytic CO insertion may also be induced by reduction. 6 The application of electrochemistry to the synthesis of organometallics and the study of organometallic reaction mechanisms is an extremely promising 'Brown University. •Deakin University.…”

Reductively induced homolytic carbon–carbon bond cleavage in Co(CO)3(PPh3)(COCF3)

“…This particular complex is one of the most thermally stable cobalt acyl complexes [2] and the trifluoromethyl group provides a convenient NMR label for following reactivity. While several examples of oxidatively and reductively induced migratory insertion reactions have been reported [3][4][5][6][7], so far as we are aware there are no examples of redox initiated decarbonylation reactions other than that of one rhenium formyl complex [8]. Though perfluoroalkyl ligands are considered unlikely to participate in migratory insertion of CO because of their relatively strong metal-carbon bonds [9], we felt that compound 1 was a good candidate for the reverse.…”