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Issue 25, 2015
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Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides

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Abstract

The synthetic and reaction chemistries of cationic iminoborylene complexes [LnM[double bond, length as m-dash]B[double bond, length as m-dash]N[double bond, length as m-dash]CR2]+, which feature a unique heterocumulene structure, have been systematically investigated. Precursors of the type CpFe(CO)2B(Cl)NCAr2 (Ar = p-Tol/Mes, 5c/d) have been generated by B-centred substitution chemistry using CpFe(CO)2BCl2 and suitable lithiated ketimines – a reaction which is found to be highly sensitive to the steric bulk at both the metal fragment and the ketimino group. Carbonyl/phosphine exchange (using PCy3 or PPh3), followed by halide abstraction allows for the generation of the cationic iminoborylenes [CpFe(PR3)(CO)(BNCAr2)]+[BArX4] (R = Cy, Ar = p-Tol/Mes, 12c/d; R = Ph, Ar = Mes, 13d; ArX = 3,5-X2C6H3 where X = Cl, CF3) which have been characterized spectroscopically and by X-ray crystallography. The reactivity of these iminoborylene systems towards a range of nucleophiles and unsaturated substrates has been investigated. The latter includes the first examples of M[double bond, length as m-dash]B metathesis reactivity with a carbodiimide, and results in Fe[double bond, length as m-dash]B cleavage and formation of the isonitrile complexes [CpFe(PCy3)(CO)(CNR)]+[BArCl4] (R = iPr/Cy, 16/17).

Graphical abstract: Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides

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Publication details

The article was received on 12 Jan 2015, accepted on 10 Feb 2015 and first published on 11 Feb 2015


Article type: Paper
DOI: 10.1039/C5DT00131E
Citation: Dalton Trans., 2015,44, 11294-11305
  • Open access: Creative Commons BY license
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    Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides

    J. Niemeyer, M. J. Kelly, I. M. Riddlestone, D. Vidovic and S. Aldridge, Dalton Trans., 2015, 44, 11294
    DOI: 10.1039/C5DT00131E

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