Synthesis, properties, and crystal structure of octaethylporphin bis[cis-dicarbonyldichlororhodate(I)][oepH4]2+2[RhCl2(CO)2]– and some new reactions of Co(oep) derivatives

Abstract

Octaethylporphin, oepH₂, and [RhCl(CO)₂]₂ react in hot chloroform to form a complex, which has been shown by chemical analysis, spectroscopic studies, and X-ray analysis to be [oepH₄]²⁺2{cis-[RhCl₂(CO)₂]}^–. Crystals are tetragonal, space group P4/n, Z= 4, with cell dimensions a= 24·604(3) and c= 8·231(1)Å. The structure has been refined by Fourier and least-squares methods to R 0·089 for l439 diffractometric intensity data. A novel feature of the structure is the essential planarity of the [oepH₄]²⁺ dication. Other new complexes to have been prepared are Co(oep)(PR₃)₂, [Co(oep)(PR₃)₂]⁺Br^–, and Co{N:C(CF₃)₂}(oep).