Structural Diversity of Iso-Maleonitrile Dithiolate d10s2 Metal Complexes of Lead and Bismuth

• Published in: Crystal growth & design Vol. 24; no. 12; pp. 5108 - 5115
• Main Authors: Ho, William W. L., Pells, Jefferson A., Leznoff, Daniel B.
• Format: Journal Article
• Language: English
• Published: American Chemical Society 19.06.2024
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/acs.cgd.4c00331

The synthesis and solid-state structures of four structurally diverse i-mnt-based anionic complexes and coordination polymers are described (i-mnt = iso-maleonitrile dithiolate). (nPr4N)4[Pb2(i-mnt)4] is dimeric, containing a five-coordinate distorted square pyramidal Pb­(II) center with a stereochemically active lone pair. The isoelectronic (nPr4N)­[Bi­(i-mnt)2] is a distorted six-coordinate complex that crystallizes in the polar P21 space group and forms a 2D coordination polymer via intermolecular Bi–N interactions; the d10s2 Bi­(III) center also has a hemidirectional coordination sphere with a stereochemically active lone pair. Using the more compact (Me4N)+ cation, (Me4N)2[Pb­(i-mnt)2] contains eight-coordinate holodirectional Pb­(II) centers that form 1D chains via bridging Pb–S bonding. These anionic complexes could provide the foundation to incorporate stereochemically active lone pairs into heterometallic coordination polymers. As a comparison, (nPr4N)3Cr­(i-mnt)3·H2O was also prepared and has a propeller structure with a typical octahedral Cr­(III) center.