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Issue 29, 2014
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Dimethylsilyl bis(amidinate)actinide complexes: synthesis and reactivity towards oxygen containing substrates

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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

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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
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    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

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