Iron diazoalkane chemistry: N-N bond hydrogenation and intramolecular C-H activation

Suzanne C. Bart; Amanda C. Bowman; Emil Lobkovsky; Paul J. Chirik

doi:10.1021/ja070056u

Iron diazoalkane chemistry: N-N bond hydrogenation and intramolecular C-H activation

Suzanne C. Bart, Amanda C. Bowman, Emil Lobkovsky, Paul J. Chirik

Research output: Contribution to journal › Article › peer-review

85 Scopus citations

Abstract

Treatment of the intermediate spin ferrous bis(dinitrogen) complex, (^iPrPDI)Fe(N₂)₂ (^iPrPDI = 2,6-(2,6-ⁱPr₂-C₆H₃NCMe₂)₂C₆H₃N), with 1 equiv of N₂CHSiMe₃ afforded the corresponding iron diazoalkane compound, (^iPrPDI)Fe(N₂CHSiMe₃). Spectroscopic studies in conjunction with the metrical parameters from the solid-state structure support an intermediate spin ferrous complex with a doubly reduced chelate and a neutral diazoalkane ligand. In solution at 23 °C, (^iPrPDI)Fe(N₂CHSiMe₃) promotes the intramolecular C-H activation of an isopropyl aryl substituent with loss of SiMe₄. Exposure of (^iPrPDI)Fe(N₂CHSiMe₃) to 1 atm of H₂ resulted in hydrogenative cleavage of the N-N and N-C bonds to yield (^iPrPDI)Fe(NH₃) and SiMe₄. Similar N-N bond cleavage chemistry was observed upon addition of hydrazine to (^iPrPDI)Fe(N₂)₂.

Original language	English (US)
Pages (from-to)	7212-7213
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	129
Issue number	23
DOIs	https://doi.org/10.1021/ja070056u
State	Published - Jun 13 2007
Externally published	Yes

All Science Journal Classification (ASJC) codes

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

Access to Document

10.1021/ja070056u

Cite this

@article{bcf1bfbc4edf406bb25eefd619b9849c,

title = "Iron diazoalkane chemistry: N-N bond hydrogenation and intramolecular C-H activation",

abstract = "Treatment of the intermediate spin ferrous bis(dinitrogen) complex, (iPrPDI)Fe(N2)2 (iPrPDI = 2,6-(2,6-iPr2-C6H3NCMe2)2C6H3N), with 1 equiv of N2CHSiMe3 afforded the corresponding iron diazoalkane compound, (iPrPDI)Fe(N2CHSiMe3). Spectroscopic studies in conjunction with the metrical parameters from the solid-state structure support an intermediate spin ferrous complex with a doubly reduced chelate and a neutral diazoalkane ligand. In solution at 23 °C, (iPrPDI)Fe(N2CHSiMe3) promotes the intramolecular C-H activation of an isopropyl aryl substituent with loss of SiMe4. Exposure of (iPrPDI)Fe(N2CHSiMe3) to 1 atm of H2 resulted in hydrogenative cleavage of the N-N and N-C bonds to yield (iPrPDI)Fe(NH3) and SiMe4. Similar N-N bond cleavage chemistry was observed upon addition of hydrazine to (iPrPDI)Fe(N2)2.",

author = "Bart, {Suzanne C.} and Bowman, {Amanda C.} and Emil Lobkovsky and Chirik, {Paul J.}",

year = "2007",

month = jun,

day = "13",

doi = "10.1021/ja070056u",

language = "English (US)",

volume = "129",

pages = "7212--7213",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "23",

}

TY - JOUR

T1 - Iron diazoalkane chemistry

T2 - N-N bond hydrogenation and intramolecular C-H activation

AU - Bart, Suzanne C.

AU - Bowman, Amanda C.

AU - Lobkovsky, Emil

AU - Chirik, Paul J.

PY - 2007/6/13

Y1 - 2007/6/13

N2 - Treatment of the intermediate spin ferrous bis(dinitrogen) complex, (iPrPDI)Fe(N2)2 (iPrPDI = 2,6-(2,6-iPr2-C6H3NCMe2)2C6H3N), with 1 equiv of N2CHSiMe3 afforded the corresponding iron diazoalkane compound, (iPrPDI)Fe(N2CHSiMe3). Spectroscopic studies in conjunction with the metrical parameters from the solid-state structure support an intermediate spin ferrous complex with a doubly reduced chelate and a neutral diazoalkane ligand. In solution at 23 °C, (iPrPDI)Fe(N2CHSiMe3) promotes the intramolecular C-H activation of an isopropyl aryl substituent with loss of SiMe4. Exposure of (iPrPDI)Fe(N2CHSiMe3) to 1 atm of H2 resulted in hydrogenative cleavage of the N-N and N-C bonds to yield (iPrPDI)Fe(NH3) and SiMe4. Similar N-N bond cleavage chemistry was observed upon addition of hydrazine to (iPrPDI)Fe(N2)2.

AB - Treatment of the intermediate spin ferrous bis(dinitrogen) complex, (iPrPDI)Fe(N2)2 (iPrPDI = 2,6-(2,6-iPr2-C6H3NCMe2)2C6H3N), with 1 equiv of N2CHSiMe3 afforded the corresponding iron diazoalkane compound, (iPrPDI)Fe(N2CHSiMe3). Spectroscopic studies in conjunction with the metrical parameters from the solid-state structure support an intermediate spin ferrous complex with a doubly reduced chelate and a neutral diazoalkane ligand. In solution at 23 °C, (iPrPDI)Fe(N2CHSiMe3) promotes the intramolecular C-H activation of an isopropyl aryl substituent with loss of SiMe4. Exposure of (iPrPDI)Fe(N2CHSiMe3) to 1 atm of H2 resulted in hydrogenative cleavage of the N-N and N-C bonds to yield (iPrPDI)Fe(NH3) and SiMe4. Similar N-N bond cleavage chemistry was observed upon addition of hydrazine to (iPrPDI)Fe(N2)2.

UR - http://www.scopus.com/inward/record.url?scp=34250866929&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34250866929&partnerID=8YFLogxK

U2 - 10.1021/ja070056u

DO - 10.1021/ja070056u

M3 - Article

C2 - 17511457

AN - SCOPUS:34250866929

SN - 0002-7863

VL - 129

SP - 7212

EP - 7213

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 23

ER -

Iron diazoalkane chemistry: N-N bond hydrogenation and intramolecular C-H activation

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this