Chelating triarylgermyl anions as ligands in lanthanide chemistry: synthesis of Ln[GeAr3]2 [Ar = C6H4(2-CH2NMe2); Ln = Sm, Yb] and the crystal structure of an unusual μ-(o-tolylene) digermane byproduct
摘要:
The synthesis of substituted triarylgermyl potassium reagents KGeAr3 [Ar = C6H4(2-CH(2)NMe(2)) and C6H3(2-OMe)(5-Me)] and their reactions with YbI2 and SmI2 are described. Clean formation of Ln[GeAr3](2) complexes is observed for Ar = C6H4(2-CH(2)NMe(2)) in which the lanthanide centre is six-coordinate with each germyl anion functioning as a tridentate ligand. Reaction of KGeAr3 [Ar = C6H3(2-OMe)(S-Me)] with LnI(2) did not produce Ln[GeAr3](2) complexes cleanly. This failure was traced to competing metallation of the diethyl ether solvent. Crystals of a mu-o-tolylenedigermane byproduct were however isolated from the YbI2 reaction and crystallographically characterized. The latter compound represents the first example of the mu-o-phenylenedigermane class of compounds to be reported.
Chelating triarylgermyl anions as ligands in lanthanide chemistry: synthesis of Ln[GeAr3]2 [Ar = C6H4(2-CH2NMe2); Ln = Sm, Yb] and the crystal structure of an unusual μ-(o-tolylene) digermane byproduct
摘要:
The synthesis of substituted triarylgermyl potassium reagents KGeAr3 [Ar = C6H4(2-CH(2)NMe(2)) and C6H3(2-OMe)(5-Me)] and their reactions with YbI2 and SmI2 are described. Clean formation of Ln[GeAr3](2) complexes is observed for Ar = C6H4(2-CH(2)NMe(2)) in which the lanthanide centre is six-coordinate with each germyl anion functioning as a tridentate ligand. Reaction of KGeAr3 [Ar = C6H3(2-OMe)(S-Me)] with LnI(2) did not produce Ln[GeAr3](2) complexes cleanly. This failure was traced to competing metallation of the diethyl ether solvent. Crystals of a mu-o-tolylenedigermane byproduct were however isolated from the YbI2 reaction and crystallographically characterized. The latter compound represents the first example of the mu-o-phenylenedigermane class of compounds to be reported.