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Title: Synthesis, structure and properties of 1,1'-diamino- and1,1'-diazidoferrocene

Abstract

We report an improved synthesis of 1,1'-diaminoferrocene, employing the reduction of 1,1'-diazidoferrocene with H2-Pd/C, along with extensive characterization data for both compounds. Diaminoferrocene under goes a reversible 1e- oxidation in CH3CN at a potential of -602 mVvs Fc0/+, one of the most negative redox potentials for a ferrocene derivative. The chemical reversibility of this process was confirmed by isolation of the stable, 17-electron[Fc(NH2)2]+ cation as PF6-, OTf-, and TCNE-salts. In the solid state, diaminoferrocene exists in two conformations: one with the NH2 groups eclipsed, and the other with the NH2 groups offset by one-fifth turn around the Cp-Fe-Cp axis. Diazidoferrocene, on the other hand, exhibits only the fully eclipsed conformation in the solid state. The Fe-Cp (centroid) vectors in the diazidoferrocene molecules are roughly aligned with the crystallographic-axis, and the molecules form layers perpendicular to this axis. The compound is thermally unstable at elevated temperatures, and rapid heating above its melting point results in explosion.

Authors:
; ; ;
Publication Date:
Research Org.:
Ernest Orlando Lawrence Berkeley NationalLaboratory, Berkeley, CA (US)
Sponsoring Org.:
USDOE Director. Office of Science. Office of Basic EnergySciences; National Science Foundation Predoctoral Fellowship
OSTI Identifier:
860717
Report Number(s):
LBNL-45723
Journal ID: ISSN 0276-7333; ORGND7; R&D Project: 404301; BnR: KC0302010; TRN: US200524%%285
DOE Contract Number:  
DE-AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 19; Related Information: Journal Publication Date: September 18,2000; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CATIONS; FERROCENE; HEATING; MELTING POINTS; OXIDATION; REDOX POTENTIAL; SYNTHESIS; VECTORS; Ferrocene

Citation Formats

Shafir, Alexandr, Power, Maurice P., Whitener, Glenn D., and Arnold,John. Synthesis, structure and properties of 1,1'-diamino- and1,1'-diazidoferrocene. United States: N. p., 2000. Web. doi:10.1021/om0004085.
Shafir, Alexandr, Power, Maurice P., Whitener, Glenn D., & Arnold,John. Synthesis, structure and properties of 1,1'-diamino- and1,1'-diazidoferrocene. United States. doi:10.1021/om0004085.
Shafir, Alexandr, Power, Maurice P., Whitener, Glenn D., and Arnold,John. Sun . "Synthesis, structure and properties of 1,1'-diamino- and1,1'-diazidoferrocene". United States. doi:10.1021/om0004085.
@article{osti_860717,
title = {Synthesis, structure and properties of 1,1'-diamino- and1,1'-diazidoferrocene},
author = {Shafir, Alexandr and Power, Maurice P. and Whitener, Glenn D. and Arnold,John},
abstractNote = {We report an improved synthesis of 1,1'-diaminoferrocene, employing the reduction of 1,1'-diazidoferrocene with H2-Pd/C, along with extensive characterization data for both compounds. Diaminoferrocene under goes a reversible 1e- oxidation in CH3CN at a potential of -602 mVvs Fc0/+, one of the most negative redox potentials for a ferrocene derivative. The chemical reversibility of this process was confirmed by isolation of the stable, 17-electron[Fc(NH2)2]+ cation as PF6-, OTf-, and TCNE-salts. In the solid state, diaminoferrocene exists in two conformations: one with the NH2 groups eclipsed, and the other with the NH2 groups offset by one-fifth turn around the Cp-Fe-Cp axis. Diazidoferrocene, on the other hand, exhibits only the fully eclipsed conformation in the solid state. The Fe-Cp (centroid) vectors in the diazidoferrocene molecules are roughly aligned with the crystallographic-axis, and the molecules form layers perpendicular to this axis. The compound is thermally unstable at elevated temperatures, and rapid heating above its melting point results in explosion.},
doi = {10.1021/om0004085},
journal = {Organometallics},
issn = {0276-7333},
number = ,
volume = 19,
place = {United States},
year = {2000},
month = {5}
}