Activator-Controlled High Temperature In-Situ Ligand Synthesis for the Formation of Rare Earth Thiolate Amide Coordination Polymers

作者：Zurawski Alexander; Wirnhier Eva; Mueller Buschbaum Klaus

来源：European Journal of Inorganic Chemistry, 2009, 2009(17): 2482-2486.

DOI：10.1002/ejic.200900208

• In situ synthesis
• Coordination polymers
• Lanthanides
• Thiolates
• C-S bond cleavage

ID rare earth thiolate amide coordination polymers can be obtained by an activator-controlled in situ ligand synthesis in reactions of molten 2-mercaptobenzimidazole with lanthanide metals. Catalytic amounts of mercury activate the metals and induce a C-S bond cleavage that in situ forms 2,2'-bibenzimidazole. The latter then reacts as a linker ligand to give (1)(infinity)[Ln(2)(MbiM)(4)(Bbim)], Mbim(-) = C(7)H(5)SN(2)(-), BbiM(2-), C(14)N(4)H(8)(2-). In addition cinnabar is formed. Stoichiometric amounts of mercury cause the complete transformation of 2-mercaptobenzimidazole to 2,2'-bibenzimidazole. Instead of thiolate coordination polymers the reaction then yields sulfur-free monomeric bibenzimidazolate complexes (BimH(2))(+)-[Ln(BbimH)(4)](-), (BimH(2))(+) = C(7)H(6)N(2)(+), BbimH(-) = C(14)N(4)H(9)(-). Thus the amount of Hg also controls the dimensionality of the products by defining the reaction path.

• 出版日期2009-6