In the Laboratory
Synthesis, Purification, and Characterization
of a µ-(1,3-Propanedithiolato)-hexacarbonyldiiron
Laboratory Experiment or Mini-Project for Inorganic Chemistry
or Integrated Laboratory
Carmen F. Works
Department of Chemistry, Sonoma State University, Rohnert Park, CA 94928; works@sonoma.edu
Many chemistry departments are beginning to offer
project-based laboratory experiences in upper-level inorganic
or integrated laboratory courses (1). Experimental projects that
incorporate several areas of chemistry are attractive both to
students and to teachers. The project described here exposes
students to biologically important transition-metal chemistry
while at the same time reinforcing traditional synthetic and
analytical techniques of inorganic chemistry. The experiment
is suitable for an upper-level inorganic laboratory or integrated
laboratory course and introduces students to air-sensitive syn-
thesis, purification, and spectroscopy of transition-metal com-
pounds.
Introduction
The iron–carbonyl compound shown in Figure 1 is the
focus of this project. µ-(1,3-Propanedithiolato)-hexa-
carbonyldiiron is a structural model for an iron-only hydro-
genase, a biological molecule found in bacteria that catalyzes
the reversible oxidation of hydrogen (2). Two different types
of hydrogenase have been described: iron–nickel and iron-only
hydrogenase (2, 3). These enzymes have bimetallic active sites
where molecular hydrogen binds. The current structural model
for iron-only hydrogenase has a reliable synthesis and purifi-
cation that is suitable for teaching undergraduate students
about air-sensitive synthesis of metal carbonyls (4). In addi-
tion to the synthesis and purification of this organometallic
compound, the characterization by spectroscopy reinforces
many important concepts taught in the fourth-year-level in-
organic chemistry course.
The steps required to complete this project are described
in detail in the Supplemental Material,W but students should
be able to independently find all aspects of the project in the
literature (3). Given the structural formula, and one week,
students can find a literature procedure for the synthesis and
purification (3). Since the students have three-hour blocks of
time, twice-a-week, it is important that their time is planned
accordingly. To help the students plan their time, they are re-
quired to submit lab plans each week that consists of (i) a
detailed experimental plan for one week (two lab periods),
Figure 1. µ-(1,3-Propanedithiolato)-hexacarbonyldiiron.
836 Journal of Chemical Education • Vol. 84 No. 5 May 2007
W
(ii) the quantity and type of chemical reagents needed for
that week, and (iii) special glassware or equipment that might
be required. This project exposes students to the following
important laboratory skills and concepts:
• Air-sensitive synthesis
• Column chromatography
• Recrystallization
• IR spectroscopy of metal carbonyls
• Optical spectroscopy of transition-metal compounds
1H
• NMR spectroscopy of transition-metal compounds
• Mass spectrometry of transition-metal compounds
Timeline
If the laboratory course has twice-a-week, three-hour
blocks of time, the synthesis, purification, and characteriza-
tion of µ-(1,3-propanedithiolato)-hexacarbonyldiiron can be
accomplished in four weeks. Each of the following points can
be completed in a three-hour lab period:
• Literature search and report (optional)
• Training on vacuum line and organization of materials
• Synthesis of iron–carbonyl compound
• Purification with toluene–silica gel column
• Purification with pentane–silica gel column
• Isolation and drying of crystals
• Optical and IR spectroscopy with extinction coefficient
measurements
• Mass spectrometry and NMR spectroscopy
Synthesis and Purification
The synthesis was successfully completed by four under-
graduate students independently. Using standard Schlenk line
techniques, Fe3(CO)12 and 1,3-propanedithiol were refluxed
under N2 in toluene for 1.5 hours. The completion of the
reaction was indicated by a color change from green to red.
When the reaction was complete, the solution was allowed to
cool to room temperature and the solvent was removed by
reduced pressure. The compound is air-stable once synthe-
sized.
Since the final compound is air-stable, purification us-
ing silica gel column chromatography was done in an open
atmosphere. The first column was eluted with toluene followed
by a second column eluted with pentane. The colored bands
and good separation allow for a clear illustration of column
• www.JCE.DivCHED.org

Table 1. Reducible and the Sum of Irreducible
Representation for CO Stretching Modes
in µ-(1,3-Propanedithiolato)-hexacarbonyldiiron
C2v E C2 σv σv’
Γ (reducible representation) 6 0 0 2
Sum of irreducible representations 2A1 + A2 + B1 + 2B2
Figure 2. Pictorial representation of the IR-active CO stretching modes
of µ-(1,3-propanedithiolato)-hexacarbonyldiiron.
chromatography. Following column chromatography the
compound was left in pentane. The volume was reduced and
the solution sat at 4 ⬚C overnight to allow for crystal forma-
tion. The compound yields brownish-red quality crystals. If
single crystal X-ray diffraction capability is available, students
should be able to solve the structure. The average student
yield for this reaction was 30% and literature yields were re-
ported to be 50% (3).
Symmetry and Group Theory
An important aspect of spectroscopy for the inorganic
chemist is the use of group theory to assign vibrational tran-
sitions in the electronic ground state of a molecule. The point
group for the iron–carbonyl molecule with the propyl bridg-
ing ligand can be approximated as C2v. It should be made clear
to the reader that this is an approximation and the molecule
will only obtain this symmetry when the propyl bridge is a
perfect triangle above the iron centers. In solution this bridge
is in consistent motion and the symmetry is lost and the mol-
ecule would properly be assigned as a C1. The symmetry analy-
sis for the CO stretches of the iron–carbonyl molecule begins
by generating a basis set of six since there are six CO ligands
in the molecule. The reducible and sum of the irreducible rep-
www.JCE.DivCHED.org • Vol. 84 No. 5 May 2007
In the Laboratory
Figure 3. IR spectrum of a 0.039 mM solution of µ-(1,3-
propanedithiolato)-hexacarbonyldiiron in toluene. Spectrum was ob-
tained using a demountable IR cell with a 0.2 mm spacer.
Figure 4. Optical spectrum of µ-(1,3-propanedithiolato)-
hexacarbonyldiiron in acetonitrile. The dashed line is a more con-
centrated solution to illustrate the shoulder at 452 nm.
resentations for the CO stretches are shown in Table 1. Of
the irreducible representations, all but A2 are IR-active, so five
peaks are predicted in the CO stretching region of the IR spec-
trum. A pictorial representation of the IR-active CO stretch-
ing modes in µ-(1,3-propanedithiolato)-hexacarbonyldiiron
is shown in Figure 2.
Spectroscopy
The IR spectrum of µ-(1,3-propanedithiolato)-hexa-
carbonyldiiron was obtained in toluene (Figure 3) but could
be obtained in a variety of organic solvents or in a KBr pel-
let. All of the modes described here are IR-active making the
assignment of each peak subtle. Because the vibrational modes
involving the largest change in dipole should be the most
intense, the peak at 2030 cm᎑1 could be assigned to a B2 tran-
sition. Using this same principle, the least intense peak at
1972 cm᎑1 could be assigned to the totally symmetric stretch,
or A1, last picture in column one of Figure 2. Firm assign-
ment of each peak CO peak cannot be made without addi-
tional experimentation or molecular modeling.
The optical spectrum of the iron–carbonyl compound
in acetonitrile is shown in Figure 4. There are two main fea-
tures: an intense band at 325 nm (1.3 × 104 M᎑1 cm᎑1) and a
• Journal of Chemical Education 837
 In the Laboratory
weaker band or shoulder around 452 nm (1.1 × 103 M᎑1
cm᎑1). The intense peak is most likely a result of charge trans-
fer (M to CO) in the molecule, and the shoulder is consis-
tent with a d–d transition.
Mass Spectrometry
The mass spectrum of the iron–carbonyl compound is
shown in Figure 5. The parent peak appears at 386 m兾z ratio
and CO-fragmentation peaks with characteristic isotope pat-
terns are observed at 358 (᎑1 CO), 330 (᎑2 CO), 302 (᎑3 CO),
274 (᎑4 CO), 246 (᎑5 CO), and 218 (᎑6 CO). The peak at
174 is consistent with Fe2S2 and 186 with Fe2S2C.
Hazards
This experiment is designed for the student in an ad-
vanced lab course. All metal carbonyl compounds should be
considered toxic and thiols are odorant. Students should be
properly trained in vacuum line techniques prior to experi-
mentation. Toluene, acetonitrile, and pentane are flammable.
Discussion
Completion of this project provides students with expe-
rience with Schlenk line techniques, purification, and spec-
troscopic characterization of metal carbonyls. In addition,
application of group theory to IR spectroscopy is illustrated.
This project is designed as an advanced lab, with little direc-
tion from the instructor, allowing students to have the respon-
sibility for experimental design, planning, and trouble
shooting. Alternatively students may be provided with the
detailed instructions found in the Supplemental Material.W
The synthesis is a one-pot reflux with color changes that
indicate the course of the reaction. The setup for the reaction
is an excellent demonstration of Schlenk line techniques and
solvent transfer under inert conditions. Students will certainly
have prior experience with column chromatography, but for
many this may be the first time they have been able to see the
separation on the column. This makes chromatography less
of a black box, and the concepts learned here can be applied
to other types of chromatography that involve colorless com-
838 Journal of Chemical Education • Vol. 84 No. 5 May 2007
Figure 5. Mass spectrum of µ-(1,3-propanedithiolato)-
hexacarbonyldiiron.
pounds or columns hidden in a box like HPLC or GC. Af-
ter two columns the compound is fairly pure and crystals are
easily obtained from pentane.
This particular iron-only hydrogenase model contains the
1,3-propanedithiol bridging ligand. Many different types of
dithiols are available, allowing a series of model compounds
to be made. If a semester-long project is desired, the synthe-
sis, purification, and characterization of these additional com-
pounds can be included.
W
Supplemental Material
Instructions for the students and notes for the instruc-
tor are available in this issue of JCE Online.
Literature Cited
1. Ball, David B.; Wilson, Randy. J. Chem. Educ. 2002, 79, 112.
2. Chen, Z.; Lemon, B. J.; Huang, S.; Swartz, D. J.; Peters, J. W.;
Bagley, K. A. Biochemistry 2002, 41, 2036–2043.
3. (a) Lyon, E. J.; Georgakaki, I. P.; Reibenspies, J. H.;
Darensbourg, M. Y. J. Am. Chem. Soc. 2001, 123, 3268–3278.
(b) Ellgen, P. C.; Gerlach, J. N. Inorg. Chem. 1973, 12, 2526–
2532.
4. Bor, G. J. Organomet. Chem. 1968, 11, 195–197.
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