Synthesis, characterization and crystal structures of organolead dithiolate compounds displaying transannular interactions DPb (D = O, S)

Treatment of Ph2PbCl2 with O(C6H4SH)2 (1a), S(C6H4SH)2 (2a) and S(C6H3SH)2O (3a) afforded the stable organolead compounds [{O(C6H4S)2}PbPh2] (1b), [{S(C6H4S)2}PbPh2] (2b) and [{S(C6H3S)2O}PbPh2] (3b). X-ray structure determinations of dithiolate-diphenyl lead compounds 1b3b revealed that the trichalcogenated ligands are tridentate in 1b and 2b, and bidentate in 3b. The lead atom acts as an acceptor atom exhibiting weak intramolecular transannular interactions with the donor D atom, with tetrahedral distortions of 48% for 1b, 51% for 2b and 45% for 3b. The local geometry at the lead atom is described as monocapped tetrahedral. The crystal packing of title compounds is stabilized by several non-bonded interactions.