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Issue 10, 2018
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Insertion, protonolysis and photolysis reactivity of a thorium monoalkyl amidinate complex

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Abstract

The reactivity of the thorium monoalkyl complex Th(CH2SiMe3)(BIMA)3 [1, BIMA = MeC(NiPr)2] with various small molecules is described. While steric congestion prohibits the insertion of N,N′-diisopropylcarbodiimide into the Th–C bond in 1, the first thorium tetrakis(amidinate) complex, Th(BIMA)4 (2), is synthesized via an alternative salt metathesis route. Insertion of p-tolyl azide leads to the triazenido complex Th[(p-tolyl)NNN(CH2SiMe3)-κ2N1,2](BIMA)3 (3), which then undergoes thermal decomposition to the amido species Th[(p-tolyl)N(SiMe3)](BIMA)3 (4). The reaction of 1 with 2,6-dimethylphenylisocyanide results in the thorium iminoacyl complex Th[η2-(C[double bond, length as m-dash]N)-2,6-Me2-C6H3(CH2SiMe3)](BIMA)3 (5), while the reaction with isoelectronic CO leads to the products Th[OC([double bond, length as m-dash]CH2)SiMe3](BIMA)3 (6) and Th[OC(NiPr)C(CH2SiMe3)(C(Me)N(iPr))O-κ2O,O′](BIMA)2 (7), the latter being the result of CO coupling and insertion into an amidinate ligand. Protonolysis is achieved with several substrates, producing amido (9), aryloxide (10), phosphido (11a,b), acetylide (12), and cationic (13) complexes. Ligand exchange with 9-borabicyclo[3.3.1]nonane (9-BBN) results in formation of the thorium borohydride complex (BIMA)3Th(μ-H)2[B(C8H14)] (14). Complex 1 also reacts under photolytic conditions to eliminate SiMe4 and produce Th(BIMA)2(BIMA*) [15, BIMA* = (iPr)NC(CH2)N(iPr)], featuring a rare example of a dianionic amidinate ligand. Complexes 2, 3, 5, 6, 11a, and 12–15 were characterized by 1H and 13C{1H} NMR spectroscopy, FTIR, EA, melting point and X-ray crystallography. All other complexes were identified by one or more of these spectroscopic techniques.

Graphical abstract: Insertion, protonolysis and photolysis reactivity of a thorium monoalkyl amidinate complex

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The article was received on 16 Dec 2017, accepted on 09 Feb 2018 and first published on 16 Feb 2018


Article type: Edge Article
DOI: 10.1039/C7SC05328B
Chem. Sci., 2018,9, 2831-2841
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Insertion, protonolysis and photolysis reactivity of a thorium monoalkyl amidinate complex

    N. S. Settineri and J. Arnold, Chem. Sci., 2018, 9, 2831
    DOI: 10.1039/C7SC05328B

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