N-Aryl Pyrrolo-tetrathiafulvalene Based Ligands: Synthesis and Metal Coordination

A straightforward general synthetic access to N-aryl-1,3-dithiolo[4,5-c]pyrrole-2-thione derivatives 6 from acetylenedicarbaldehyde monoacetal is depicted. In addition to their potentiality as precursors to dithioalkyl-pyrrole derivatives, thiones 6 are key building blocks to N-aryl monopyrrolo-tetrathiafulvalene (MPTTF) derivatives 10. X-ray structures of four of these thiones intermediates, reminiscent of the corresponding MPTTF derivatives, are provided. When the aryl group is a binding pyridyl unit, the MPTTF derivative 10a can coordinate M(II) salts (M = Pt, Pd). The first examples of metal-directed orthogonal MPTTF-based dimers 11−14, obtained through coordination of 10a to cis-blocked square planar Pt or Pd complexes are described. Studies on the parameters influencing the dimer construction are presented, as well as first recognition properties of the resulting electron-rich clip for C60.