Jump to main content
Jump to site search

Issue 29, 2014
Previous Article Next Article

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

Author affiliations

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 ThCl4(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 [(CH3)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.

Graphical abstract: Dimethylsilyl bis(amidinate)actinide complexes: synthesis and reactivity towards oxygen containing substrates

Back to tab navigation

Supplementary files

Publication details

The article was received on 07 May 2014, accepted on 04 Jun 2014 and first published on 09 Jun 2014


Article type: Paper
DOI: 10.1039/C4DT01361A
Citation: Dalton Trans., 2014,43, 11376-11387
  •   Request permissions

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

    I. S. R. Karmel, T. Elkin, N. Fridman and M. S. Eisen, Dalton Trans., 2014, 43, 11376
    DOI: 10.1039/C4DT01361A

Search articles by author

Spotlight

Advertisements