Dimethylsilyl bis(amidinate)actinide complexes: Synthesis and reactivity towards oxygen containing substrates

Isabell S.R. Karmel, Tatyana Elkin, Natalia Fridman, Moris S. Eisen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

Abstract

The reactivity of the monoanionic amidinate ligand [(CH3) 3CNC(Ph)NSiMe2NC(Ph)-NHC(CH3)3]Li (1) with a silyl amido side arm towards the early actinides, uranium and thorium, was investigated. While the salt metathesis reaction with ThCl 4(thf)3 afforded the bis(amidinate)thorium(iv) dichloride complex [(CH3)3CNC(Ph)NSi(CH3) 2NC(Ph)-NHC(CH3)3]ThCl2 (2) in high yield, the reaction of ligand 1 with UCl4 leads to a Lewis acid supported nucleophilic attack of an incoming ligand unit, yielding the trichloro uranium complex [(CH3)3CNC(Ph)Si(CH3) 2-N(C(CH3)3)C(Ph)NSi(CH3) 2NC(Ph)N-(C(CH3)3]UCl3 (4). The exposure of in situ formed complex 2 to wet THF solutions (<1% w of water), gave the mono(amidinate)Th(iv)(chloro)(bis-hydroxo) dimeric complex [(CH 3)3CNC(Ph)NSiMe2NC(Ph)NHC(CH3) 3Th(OH)2(Cl)]2·(3) as bright red needles, exhibiting extremely short Th-OH bond distances (1.741(5) Å and 1.737(5) Å). The reactivity of the thorium complex 2 in the ring opening polymerization (ROP) was studied, showing high activity. Thermodynamic and kinetic measurements were performed to shed light on the mechanism for the ROP. This journal is

Original languageEnglish
Pages (from-to)11376-11387
Number of pages12
JournalDalton Transactions
Volume43
Issue number29
DOIs
StatePublished - 7 Aug 2014
Externally publishedYes

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