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Issue 26, 2014
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Generation of low-valent tantalum species by reversible C–H activation in a cyclometallated tantalum hydride complex

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Abstract

The cyclometallated tantalum(V) hydride complex {ArNC(Me)CHC(Me)N[2-(CHMeCH2)-6-iPr-C6H3]}Ta(NtBu)H (2) was prepared from hydrogenolysis of (BDI)TaNtBuMe2 (BDI = N,N′-diaryl-β-diketiminate, aryl = 2,6-iPr2-C6H3). Based on mechanistic studies, formation of 2 likely proceeds through a dihydride intermediate generated from successive σ-bond metathesis steps. Compound 2 was found to undergo reductive elimination under certain conditions to form trivalent tantalum species. Coordination of DMAP to 2, followed by gentle heating under H2, gives (MAD)Ta(NtBu)(NAr)(DMAP), which is produced through reductive C–N bond cleavage of the BDI ligand in a Ta(III) intermediate. Ta(III) dicarbonyl derivatives have been accessed by either introducing CO atmosphere to the DMAP adduct of 2 at room temperature, or by directly adding CO to 2 at low temperature.

Graphical abstract: Generation of low-valent tantalum species by reversible C–H activation in a cyclometallated tantalum hydride complex

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Publication details

The article was received on 28 Mar 2014, accepted on 16 May 2014 and first published on 19 May 2014


Article type: Paper
DOI: 10.1039/C4DT00923A
Dalton Trans., 2014,43, 10046-10056

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    Generation of low-valent tantalum species by reversible C–H activation in a cyclometallated tantalum hydride complex

    B. M. Kriegel, R. G. Bergman and J. Arnold, Dalton Trans., 2014, 43, 10046
    DOI: 10.1039/C4DT00923A

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