N_2 Functionalization at Iron Metallaboratranes
- Creators
- Moret, Marc-Etienne
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Peters, Jonas C.
Abstract
The reactivity of the anionic dinitrogen complex [(TPB)Fe(N_2)]^− (TPB = tris[2-(diisopropylphosphino)phenyl]borane) toward silicon electrophiles has been examined. [(TPB)Fe(N_2)]^− reacts with trimethylsilyl chloride to yield the silyldiazenido complex (TPB)Fe(NNSiMe_3), which is reduced by Na/Hg in THF to yield the corresponding sodium-bound anion [(TPB)Fe(NNSiMe_3)]Na(THF). The use of 1,2-bis(chlorodimethylsilyl)ethane in the presence of excess Na/Hg results in the disilylation of the bound N_2 molecule to yield the disilylhydrazido(2−) complex (TPB)Fe≡NR (R = 2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl). One of the phosphine arms of TPB in (TPB)Fe≡NR can be substituted by CO or ^tBuNC to yield crystalline adducts (TPB)(L)Fe≡NR (L = CO, ^tBuNC). The N–N bond in (TPB)(^tBuNC)Fe≡NR is cleaved upon standing at room temperature to yield a phosphoraniminato/disilylamido iron(II) complex. The flexibility of the Fe–B linkage is thought to play a key role in these transformations of Fe-bound dinitrogen.
Additional Information
© 2011 American Chemical Society. Received: September 14, 2011. Publication Date (Web): October 18, 2011. This work was supported by the NIH (GM 070757). M.-E.M. acknowledges a Fellowship for Prospective Researchers from the Swiss National Science Foundation. We thank Charlene Tsay and Larry Henling for crystallographic assistance, as well Angelo Di Bilio for assistance with EPR measurements.Attached Files
Supplemental Material - ja208675p_si_001.pdf
Supplemental Material - ja208675p_si_002.cif
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Additional details
- Eprint ID
- 28664
- DOI
- 10.1021/ja208675p
- Resolver ID
- CaltechAUTHORS:20120105-085838649
- NIH
- GM 070757
- Swiss National Science Foundation (SNSF)
- Created
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2012-01-05Created from EPrint's datestamp field
- Updated
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2021-11-09Created from EPrint's last_modified field