Synthesis and Structural Characterization of Homo‐ and Heterometallic Li and Li/ Ln Disiloxanediolate Complexes

A series of new homo‐ and heterometallic lithium and lithium/lanthanide disiloxanediolate complexes were prepared and fully characterized. Three new adducts of dilithium tetraphenyldisiloxanediolate, [(Ph 2 SiOLi) 2 O] ( 2 ), with simple Lewis bases (Et 2 O, THF, DME) were prepared by treatment of Ph 2 Si(OH)OSiPh 2 (OH) ( 1 ) with 2 equiv. of n ‐butyllithium in the respective donor solvent. This way the adducts [{Ph 2 SiOLi(Et 2 O)} 2 O] 2 ( 3 ), [{Ph 2 SiOLi(THF)} 2 O] 2 ( 4 ), and [{Ph 4 Si 2 O(OLi) 2 } 2 (DME) 3 ] ∞ ( 5a ) were obtained in a straightforward manner and in nearly quantitative yields. Treatment of anhydrous lanthanide(III) chlorides Ln Cl 3 ( Ln = Tb, Lu) with 2 equiv. of 2 in THF afforded the new lanthanide(III) bis(disiloxanediolate) complexes [{(Ph 2 SiO) 2 O} 2 {Li(THF) 2 } 2 ]TbCl ( 6 ) and [{(Ph 2 SiO) 2 O} 2 {Li(THF) 2 } 2 ]LuCl ( 7 ) in high yields. Similar reactions of Ln Cl 3 ( Ln = Ce, Nd) with 3 equiv. of 2 provided the heterometallic Li/ Ln tris(disiloxanediolate) complexes [{(Ph 2 SiO) 2 O} 3 {Li(DME)} 2 {Li(THF)}]Ce ( 8 ) and [{(Ph 2 SiO) 2 O} 3 {Li(DME)}{Li(Et 2 O)}{Li(THF)}]Nd ( 9 ). All title compounds were structurally characterized through single‐crystal X‐ray diffraction.