Mixed-Donor Amido-Siloxo Actinide(IV) Halide and Alkyl Complexes with an Aryl C-ipso Interaction

作者：Hayes Cassandra E; Gill Dayle E; Brown Matthew L; Leznoff Daniel B^*

来源：European Journal of Inorganic Chemistry, 2014, 2014(23): 3690-3700.

DOI：10.1002/ejic.201402226

• Actinides
• Uranium
• N ligands
• Mixed-donor ligands
• Siloxo donors

The synthesis and characterisation of a series of new actinide(IV) complexes supported by the mixed-donor amido-amino-siloxo framework [RN(Li)SiMe2N(R)SiMe2OLi] ([(NNO)-N-R]Li-2; R = 2,4,6-Me3Ph, 2,6-iPr(2)Ph) are presented. The reaction of 1 equiv. of [(NNO)-N-R]Li-2 with ThCl4 center dot 2DME (DME = 1,2-dimethoxyethane) in DME generated {Li center dot nDME}{[(NNO)-N-R](2)Th2Cl5} (1: R = 2,4,6-Me3Ph, n = 2; 2: R = 2,6-iPr(2)Ph, n = 3) in high yield, and the addition of [(NNO)-N-Me3Ph]Li-2 to UCl4 in tetrahydrofuran (THF) resulted in the formation of {[(NNO)-N-Me3Ph]UCl3Li center dot THF}(2) (3). The structures of 1-3 indicate that they retain LiCl as "ate" complexes. The addition of 2 equiv. of [(NNO)-N-Me3Ph]Li-2 to ThCl4 center dot 2DME and UCl4 gives the bis-ligated complexes [(NNO)-N-Me3Ph](2)ThClLi (4) and [(NNO)-N-Me3Ph](2)U (5), respectively. In 1-5, the [(NNO)-N-R](2-) ligands all coordinate through the amido and siloxo donors as well as the ipso carbon atom of the phenyl group of the amido ligand but not through the central amino group. Complex 3 can be alkylated through the addition of 2 equiv. of LiCH2SiMe3 to give [(NNO)-N-Me3Ph]U(CH2SiMe3)(2) (6) or NaCp (Cp = cyclopentadienyl) to give [(NNO)-N-Me3Ph]UCp2 (7); the latter has been structurally characterised.

• 出版日期2014-8