Homoleptic Trigonal Planar Lanthanide Complexes Stabilized by Superbulky Silylamide Ligands

作者：Goodwin Conrad A P; Joslin Kristian C; Lockyer Selena J; Formanuik Alasdair; Morris Gareth A; Ortu Fabrizio; Vitorica Yrezabal Inigo J; Mills David P^*

来源：Organometallics, 2015, 34(11): 2314-2325.

DOI：10.1021/om501123e

The lithium silylamides [Li(mu(3)-NHSiMe2But)](6) (1) and [Li(mu-NHSiPr3i)(THF)](2), (2) were reacted with ClSiMe3, ClSiMe2But, or ClSiPr3i to prepare a series of secondary silylamines by salt metathesis reactions. These were deprotonated with KH to afford the group 1 transfer agents [K{mu-N(SiMe2But)(SiMe3)/(C7H8)L (3), [{K[mu-N(SiPr3i)(SiMe3)]}(2)](infinity), (4), [{K[mu-N(SiMe2But)(2)]}(2)(C7H8)](infinity) (5), [K{N(SiPr3i)(SiMe2But}](infinity) (6), [KN(SiPri)(2)}](infinity) (7), and [K{N(SiPr3i)(2)}(THF)(3)] (8). The synthetic utility of these group 1 transfer agents has been denionstrated by their reactions with [Ln(I)(3)(THF)(4)] (Ln = La, Ce) In various stoichiometries to yield heteroleptic [La{N(SiMe2But)(SiMe3)}(2)(mu-I)](2) (9), and homoleptic [Ln{N(SiMe2But)(SiMe3)}(3)]. (Ln = La 10, Ce 11) and [La{N(SiMe2But)(2)}(3)] (12). The very-bulky silylamide ligands described herein can impart unusual geometries to their lanthanide complexes. Complexes 10-12 remarkably exhibit approximate planarity in the solid state rather than the more common trigonal pyramidal shapes, observed in previously reported neutral homoleptic lanthanide silylamide complexes. Complexes 1-12 have been variously characterized by X-ray crystallography, NMR spectroscopy, FTIR spectroscopy, and CHN microanalysis.

• 出版日期2015-6-8