Jump to main content
Jump to site search

Issue 26, 2014
Previous Article Next Article

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

Author affiliations

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

Back to tab navigation

Supplementary files

Article information


Submitted
28 Mar 2014
Accepted
16 May 2014
First published
19 May 2014

Dalton Trans., 2014,43, 10046-10056
Article type
Paper

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

Social activity

Search articles by author

Spotlight

Advertisements