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Issue 18, 2017
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An amidato divalent ytterbium cluster: synthesis and molecular structure, its reactivity to carbodiimides and application in the guanylation reaction

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Abstract

A divalent ytterbium amidate 1 ([Yb3L6]·2C7H8 for short) was synthesized via amine-elimination of Yb[N(SiMe3)2]2(TMEDA) with an amide proligand N-2,6-diisopropylphenylbenzamide HL (L = 2,6-iPr2C6H3NC(O)Ph) and structurally characterized to be a trinuclear symmetric cluster. Further studies on the reduction of iPrN[double bond, length as m-dash]C[double bond, length as m-dash]NiPr by complex 1 provide Yb(III) complex 2 in hexane–THF ([(YbL2)2(μ-NiPrCNiPr)][YbL3(THF)]·C7H8), which is composed of two subunits in a unit cell, one is a bridged Yb(III) carbene, just the same as complex 4 ([(YbL2)2(μ-NiPrCNiPr)]·3C7H8) obtained in the same reaction in toluene, and the other is a homoleptic monomeric Yb(III) amidate (YbL3). It is also found that complex 2 decomposed to complex 3 ([YbL3]2·2C7H8) and 4 at 90 °C in toluene. Complexes 1–4 were confirmed by X-ray structure determination. Furthermore, complex 4 was proved to be a more active species than its precursor 1 in the catalytic addition of amines to carbodiimides. Finally, complex 1 was found to be an excellent pre-catalyst for the guanylation reaction with a wide scope of substrates.

Graphical abstract: An amidato divalent ytterbium cluster: synthesis and molecular structure, its reactivity to carbodiimides and application in the guanylation reaction

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Publication details

The article was received on 10 Mar 2017, accepted on 30 Mar 2017 and first published on 20 Apr 2017


Article type: Paper
DOI: 10.1039/C7DT00871F
Citation: Dalton Trans., 2017,46, 6031-6038
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    An amidato divalent ytterbium cluster: synthesis and molecular structure, its reactivity to carbodiimides and application in the guanylation reaction

    C. Gong, H. Ding, C. Lu, B. Zhao and Y. Yao, Dalton Trans., 2017, 46, 6031
    DOI: 10.1039/C7DT00871F

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