48243-45-4Relevant academic research and scientific papers
Synthesis, structure, and unusual reactivity of β-halovinyl cobalt porphyrin complexes
Fritsch, Joseph M.,Retka, Noah D.,McNeill, Kristopher
, p. 2288 - 2295 (2006)
The preparation, structures, and reactivity of tetraphenylporphyrin (TPP) cobalt halovinyl complexes are reported. β-Halovinyl complexes of (TPP)Co(E-CHCHX) (X = Br and I) were prepared from the insertion of acetylene into the cobalt halide bonds of the corresponding halide complexes. The reactivity of these compounds and of the previously reported (TPP)Co(E-CHCHCl), was studied in depth, and it was found that complex reactivity increased with the leaving group ability of the halide. A trans-dichlorovinyl cobalt porphyrin complex, (TPP)Co(Z-CClCHCl), was also prepared through the reaction of (TPP)CoNa and TCE. The structures of (TPP)Co(E-CHCHBr), (TPP)-Co(Z-CClCHCl), and (TPP)Co(C2H) are reported. The C-C bond length of the vinyl group was found to vary for the β-halovinyl complexes (TPP)Co(E-CHCHX) from 1.211 A for X = Br to 1.234 A for X = Cl and 1.320 A for (TPP)Co(Z-CClCHCl). A comparison of these structures to many chlorovinyl cobalt complexes shows that trans2-halo substitution results in a dramatically decreased vinyl C-C bond length. The mechanism of halide substitution for the β-halovinyl complexes was investigated with kinetic experiments that indicated a dissociative mechanism and supported the intermediacy of a cobalt acetylene complex.
