Activation of Ancillary Ligands in the Reactions of DMAD with Phosphido and Alkylideneamido Rhenium Complexes

As an extension of previous work, the reactions of dimethylacetylenedicarboxylate (DMAD) with the
phosphido complex [Re(PPh2)(CO)3(phen)] (1) and the
alkylideneamido [Re(NCPh2)(CO)3(bipy)] (2) were investigated. The characterization of the products by
spectroscopy (IR and NMR) and X-ray diffraction revealed the coupling between DMAD, the phosphido or
alkylideneamido group, and the phenanthroline (in the
reaction of 1) or one of the carbonyl (in the reaction of 2)
ligands, in a way consistent with initial attack of the P
in 1 (or the N in 2) on one of the acetylenic carbons of
DMAD.