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N_2 Functionalization at Iron Metallaboratranes

Moret, Marc-Etienne and Peters, Jonas C. (2011) N_2 Functionalization at Iron Metallaboratranes. Journal of the American Chemical Society, 133 (45). pp. 18118-18121. ISSN 0002-7863.

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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.

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Peters, Jonas C.0000-0002-6610-4414
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.
Funding AgencyGrant Number
NIHGM 070757
Swiss National Science Foundation (SNSF)UNSPECIFIED
Issue or Number:45
Record Number:CaltechAUTHORS:20120105-085838649
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Official Citation: N2 Functionalization at Iron Metallaboratranes Marc-Etienne Moret and Jonas C. Peters Journal of the American Chemical Society 2011 133 (45), 18118-18121
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:28664
Deposited By: Ruth Sustaita
Deposited On:05 Jan 2012 17:14
Last Modified:26 Nov 2019 11:15

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