The Modern Student laboratory

Photochemical and Electrochemical Studies

of an Organometallic Sandwich Compound
An Inorganic Chemistry Experiment
David C. Boyd
University of St. Thomas, St. Paul, MN 55105
Brian J. Johnson
St. John's University, Collegeville. MN 56321
Kent R. ~ a n n '
University of Minnesota, Minneapolis, MN 55455
The field of organometallic chemistry has developed rap- Further, the experiment is an example of an "integrated"
idly since the synthesis and characterization of f e m e n e laboratory exercise. A compound is synthesized and then
in the early 1950's. In particular, cyclic n-donor complexes studied by several complementary techniques. The data is
of the transition metals constitute an important class of then analyzed in order to draw mechanistic conclusions
organometallic molecules. about the reactions under investigation.
This experiment gives the student an opportunity to syn- The open-ended nature of the experiment allows it to be
thesize and study a representative member of this family, carried out in two 4-h periods, or more if desired. Conceiv-
the iron(I1)sandwich compound ably the experiment could serve as the framework for an
entire term of lab work in which the students formulate a
[CpFe(tal)lPF, mini research project.
containing cyclopentadienyl and toluene ligands, where
Cp is qS-C5H5and to1 is $-toluene. Theory
This compound undergoes photochemical disproportion- The Reactions
ation (I)in neat acetonitrile solution to produce
In 1970, Nesmeyanov and coworkers reported that the
ferrocene (FeCpz) photolysis of an acetonitrile solution of [CpFe(arene)l+pro-
solvated iron(I1)as [F~(cH~cN)& duced solvated Fe(I1) and ferrocene in equimolar quanti-
free toluene ties (1).A detailed investigation of this reaction revealed
Because all of the iron-containing species are electrochem- that a purple photointermediate [CpFe(CH3CN)31+could
icallv active. the course of the reaction may be monitored be characterized at -40 O C (3).Upon warming, the purple
by cyclic voltammetry. species decomposed to form the final products.
If added ligands such as -phosphines,
-
phosphites, or isocyanides were present,
substituted complexes of the type
20°c, L [c~F~(L)~(cH~cN)]+ [CpFe(CH3CN)3..(L),I+ were isolated (I,

[Fe(phen)J2+ - 20°c
hv
phen
-
[CpFe(tol)]+
720 O c
twarm to ~o'c,L

+
[CpFe(CH3CN)d++ toulene
warm to 20°c. L
4). Chelating ligands such a s
phenanthroline (phen) react with the
photogenerated [Fe(CH3CN)61Z+ or
[CpFe(CH3CN)31+to form the deep-red
complex [Fe(phen)312+,but they do not
hv read with ferrocene.
These reactions are summarized in Fig-
ure 1. Electrochemistrv... in -particular cv-
1/2FeCp2+ l/2[Fe(phen)d2+ clic voltammetry, is a very useful tool &I
I the characterization of these complexes.
In this experiment, students examine
Figure 1. Summary of reactions of [CpFe(tol)lt some of the photochemical reactions
shown in Figure 1. Electrochemistry is
An Integrated and Open-Ended Project used to identify the reaction products and to formulate a
Despite the widespread application of photochemistry mechanism for the photolyses.
and electrochemistry in research, the disciplines have re-
ceived relatively little attention in the undergraduate inor- Introductory Literature
ganic laboratory (2). This experiment is designed to fill
that gap. Before beginning the experiment, the students become
familiar with the principles underlying the reactions and
'Author to whom corresoondence should be addressed concepts to be be used. Introductory material describing
(Continued on page A3161
Volume 69 Number 12 December 1992 A315
The Modern Student lclborcltory

basic concepts of photochemistry and electrochemistry are Any resulting chunks should be broken up with a glass rod.
included in the student lab manual and reviewed in the As much solid a s possible is transferred from the round-
prelab lectures. Several suitable reviews appropriate for bottom flask to the-hydrolysis flask. The resulting mixture
this introduction have been published previously (5-11). is then transferred to a separatory funnel.
In the funnel, the yellow or yellow-green aqueous layer
Experimental containing the product is separated from the organic layer.
Reagents Ascorbic acid (0.5 g) is added to the mixture to reduce any
ferricinium ion (lFeCpz+l)to ferrocene. The aqueous layer
The synthesis and electrochemical measurements de- is extracted with three 25-mL portions of hexane to remove
scribed in this paper are relatively insensitive to chemical ferrocene and then slowly suction-fdtered to remove the
made or oriein. With the excention of the anhvdrous alu- remaining aluminum metal. Asolutiou of 2 g W F 6 in 10
H n u m chlozde (which should be fresh) and thlelectrolyte
(which was dried as described below).
purification is required.
- .-
..no reaeent drvine or
mL of water is added gradually to the filtrate with stirring
to form a yellow precipitate of crude [CpFe(tol)lPF6.
If the mother liquor is still quite yellow, more W F 6
may be added. Stir for about 10 min, suction-filter, and
Electrochemical Measurements allow to air-dry. The yield of crude product is about 75%.
Electrochemical measurements were carried out under
an inert atmosnhere with a Bioanalvtical Svstems CV-1B ElectrochemicalAnalysis
(SJU) or CV-~~'(usT and UM)on soiutions Laving a n iron The product is purified before carrying out electrochem-
comnlex concentration of 5 x lo3 M. A three-electrode con- ical measuremenis by allowing a CH& solution to pass
figuration was used in all experiments. through a short (10-cm) column of F-20 alumina. The col-
'glassy-carbon electrode umn is wranned with aluminum foil to avoid nroloneed ex-
platinum-wire auxiliary electrode posure of t6; solution to room light. The vol-e oceluted
aqueousAgCVAg reference electrode containing 1.0 M KC1 solution is reduced to about 5 mL. and the vellow micro-
crystalline product is precipitated kith diethi1 ether.
The solvent/sunnortine electrolvte svstem consisted of a
0.1 M solution of'tktra-nTbutyla-o& hexafluorophos- Analytical Data
hate (TBAH) (Southwestern Analvtical or Aldrich) in
&e&ly distilled reagent-grade aceto&trile. The electrolyte
solution was dried over 80-200-mesh activated alumina
before use. All potentials a m reported versus AgCVAg. The
[FeCpzTFeCp, couple was observed at +0.520 V in the ex- Results and Discussion
periGnta1 system used to generate the figures. This experiment frequently occupies two or three periods
of an advanced inorganic laboratory course. The first pe-
Photochemical Experiments riod is devoted to preparation and purification of the sand-
Caution:Despite the Pyrex filtering it is harmful to look at wich compound, while the electrochemistry and photo-
Hg radiation. The lamp should be screened from direct view. chemistry experiments require one or two lab periods as
scheduling permits.
Photochemical experiments were carried out with the F e m n e is used a s a "warm UD"compound d u r i w the
Pyrex-filtered output of a 150-W Hg street lamp modified laboratory session devoted to ele&oche&stry in ord'kr to
on site. However, any source of visible light will suffice. familiarize the student with the equipment. The photo-
chemical experiments are carried out in one or two subse-
Preparation of [CpFe(tol)]PFe quent laboratory sessions. If three lab periods are not
Caution:Aluminum chloride is corrasive and moisture-sen- available. the instructor can c a m out one or more ~hotol-
sitive. ysis expekments and then give k e data to the students. In
this wav. the students mav draw mechanistic conclusions
Synthesis about tKe system even iftlme precludes collection of a full
[CpFe(tol)lPF6was prepared by a modification of the data set.
method of Nesmeyanov e t al. ( I ) . A 3-necked 250-mL The initial electrochemical investigation of ferrocene
round-bottom flask equipped with a magnetic stir bar, ni- serves three purposes.
trogen inlet, and reflux condenser connected to a mineral
oil bubbler is assembled and then purged with nitrogen for The exercise familiarizes the student with the instrumenta-
tion and techniques used in electzochemical studies.
5 min. *The student gains experience with one of the products
With the nitrogen off, 2.5 g of ferrocene, 0.5 g aluminum iFeCpz)produced in the photolysis of [CpFe(tol)l+.
powder, 5.0 g aluminum chloride, 50 mL toluene, and 0.25 .The student then collects data for numerical analysis and
mL of water are added. The mixture is refluxed for 2 h with discussion.
stirring under a slow stream of nitrogen. After refluxing,
the dark-brown solution is cooled and may be stored in the Scan-Rate Study
dark for up to a week with no ill effects.
The students investigate the basic principles of cyclic
Workup voltammetry and the influence of scan rate on a cyclic
The migture is then hydrolyzed by pouring it, with stir- voltamrnograrn by carrying out a scan rate study on ferro-
ring, into 100 mL of a water-ice mixture in a fume hood. (Continuedon page A318)

A316 Journal of Chemical Education

 The Modern Student laboratory

cene. The numerical results from each scan rate are ana-
lyzed and tabulated to yield the following information.

scan rate lP peak potentiah

peak currents
peak separation
the number of electrons associated with the proeess
(as calculated from the Randles-Sevick equation (11))
.student plots of i, vs. vm.
This exercise leads to a discussion of topics such as rate
of electron transfer, the characteristics of a ureversible"
system, and the Nernst equation.
ElectrochemicalStudy
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After studying the redox chemistry of f e m e n e , the stu-

dents turn to a n electrochemical studv of the irreversible
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Fe(II)/Fe(I) process of [CpFe(tol)lt ( k g . 2a). The cyclic

voltammogram of [CpFe(tol)lt provides a basis for discus-
sion of several topics.
the influence of Ligands on metal-based redox reactions
radical lifetime versus the time scale of the experiment
graphical and numerical features of an irreversiblecouple
For example, when a Cp-ligand of ferrocene is replaced
with a toluene group to form [CpFe(tol)l+,the potential of
the Fe(III)/Fe(II) couple shifts to positive values beyond
the solvent window, and thus is not observed. When com-
pared to FeCpz, this represents a shiR of a t least 1.6 V to a
more positive potential due to the electronic difference be-
tween toluene and Cp-. The Fe(II)/Fe(I) reductive couple of
[CpFe(tol)l+( E , , = -1.355 V) exhibits a similar shiR rela-
tive to FeCp, and is now observed within the solvent win-
dow. The Fe(II)/Fe(I) reduction of [CpFe(tol)ltbecomes re-
versible a t 4 0 "C (12).
This exoeriment mav be carried out (as time oermits). bv"
placing the electrochemical cell in an acetonitrile-dry-ice
bath and recording the cyclic voltammogram. Observation
of this phenomenon facilitates a discussion of the relation-
ship between the lifetime of an intermediate species and
temperature. The reduction of other [CpFe(arene)lt com-
~ l e x e sleads to the formation of more-stable Fe(1) radical
species (13). E IUOLT I
The Photolysis Reactions Figure 2. (a)Cyclic voltammogram obtained from 10.0 mL of 5 mM
[CpFe(tol)]+in 0.1 M CHBCNfrBAHat a scan rate of 0.200 Vls. (b)
Formation of[FeCp8 and Iron Film Cyclicvoltammogram ofthe solution from Figure Zamllected after 15
Photolysis of [CpFe(tol)li in neat CH&N solution or in min of photolysis. (c)Cyclic voltammogram of the solution from Fig-
the Dresence of added nucleo~hilesresults in the reactions ure 2a collected after 40 min of photolysis. (d) Photolyzed solution
from Figure 2c after adding 14.0 mg 1,lO-phenanthroline.
outlked in Figure 1.~ i g u r e h and
b 2c are examples of the
cyclic voltammograms obtained as [CpFe(tol)l+is photo-
chemically converted to products in CHsCN/TBAH.
(For example, the fdm can be removed by wiping the elec-
- .
As the ~hotolvsisconsumes ICoFe(tol)l+. a decrease in
current for t h ~ s~rrevcrslblereduction 1s ubserved Con- trode with a n acetone-soaked tissue.) Failure to completely
comltant with the loss of reductlvc current for ICoFe(tnl11- remove this film will result in broad, featureless waves
. ~.
that are very difficult to interpret.
. &

is the appearance of a quasireversible one-electron oxida-

tion (+0.520 V; oxidation of FeCpz to [FeCp21+)and a n ir- Formation of [~e(~hen)d'+
regularly shaped, irreversible two-electron reduction
(-1.020 V; reduction of solvated Fe(I1) to Fe(0)) due to the Phenanthroline (14 me) is added to the solution at the
newly formed photoproducts. end of the photolysis res&ing in formation of [Fe(phen)JZ+
The new two-electron reductive wave represents reduc-
tion of solvated Fe(I1) to a passivatingiron metal film that
-
from the solvated Fe(I1) (Fie. 2d). The cvclic voltammo-
gram now shows a new quasireverslble one-electron oxida-
deposits on the electrode surface. One must remove this tive couple at +1.255 V due to the FetII~tnFe(I1IJoxidation
film after each scan in order to obtain high-quality data. of the deep-red complex [Fe(phen)dh. The cathodic pro-

A318 Journal of Chemical Education

 When phenanthmline is added before photolysis, cyclic
voltammetry shows that no thermal reaction occurs. Sub-
sequent photolysis of [CpFe(tol)l+in the presence of phen
results exclusively in formation of [Fe(phen)312t(Fig.3) as
indicated by the oxidation and reduction processes ob-
sewed a t +1.2255 V and -1.40 V, respectively. This result
indicates that the ~ r e c e d i mechanism
n~
absence of ligandsother t h i n solvent.
..
aoolies onlv in the
(This photolysis will not run to completion in this wn-
centration regime due to an inner filter effect imposed by
the strongly absorbing l F e ( ~ h e n ) ~compound.
l~+ The stu-
dents should be told this so they will not have to wait for
all IC~Fe(tol)l+ to be consumed.)
~ t u i e n t sare able to rationalize this result by arguing
that ~henanthrolinetram the ~botointermediatebefore
the disproportionation t#;fermceeneand solvated Fe(I1) oc-
curs. Thus the left-hand side of Firmre- 1 has been 'discov-
ered".
Flexibility in the Project
Figure 3. Cyclic voltammogram obtained from 10.0 mL of 5 mM This laboratory is sufliciently open-ended that students
[CpFe(tol)]+ in 0.1 M CH3CNlTBAHwllected after 60 min of photoly- can pursue "mini research projects" simply by augmenting
sis in the presence of 30 mg of 1,lo-phenanthroline at a scan rate of
0.200 v/s.
or otherwise modifving the analvsis . -~rocedure.
For example, an-emphasis on synthetic chemistry may
be achieved using different arenes as the solvent in the
cesses between -1.00 V and -1.500 V are due to reduction synthesis portion of the experiment to yield the corre-
of the phen moities in lFe(phed312+to coordinated radical sponding - [CpFe(arene)l+
. compounds. Then students can
anions. The peak current for the oxidation of [Fe(phen)312+ ail prepare and characterize &eir own wmpound or series
is approximately equal to that for the oxidation of FeCp2 of compounds.
leading to the conclusion that FeCp2 and [ ~ e ( p h e n ) ~ l ~ ' Alternatively, students can prepare compounds of the
(and therefore solvated Fe(I1)) are produced in equal pm- formula
portions. [CpFe(CH3CN)L2It
Identifying the Products by photolyzing in the presence of the appropriate phos-
phite ligand, where L is P(OPb)3or P(OMe)3.
The initial study of FeCp,will allow the student to iden- Advanced techniaues such as m s t a l erowth bv slow sol-
tify this compound as a photoproduct, while solvated Fe(I1) vent diffusion are readily added tdthe Gocedure Layering
may be identified by derivatization with phenanthroline. a concentrated C H X L solution of the arene comolex with
When phenanthroline is added, [ F e ( ~ h e n ) ~may l ~ +be iden- ether is an effective c&stal-growth wmbination, but other
tified from the characteristic red color encountered in pre- combinations work as well.
vious lab work, or by examining the reaction stoichiometry
and appling the 18-electron rule. Literature Cied
Nevertheless, the students are able to postulate the 1.Nesmeyanov,A N.; Vi%au,N.A.; Shiloutseva,L. S.Dokl.Akod NouhSSSR 1910,
mechanism below or some variation of it by using some 190,857.
2. Please see the exeellmt %ate of the Art' seriea on Inorganic Photoehemistry lo J
combination of the following strategies and facts. ChPm Ed=. 1889,60.785-887.
3. Gill, T. P ; Mann, K R. I n o g ChPm 1 ~ , 2 2 , 1 9 8 6 1 9 9 1 .
experimental observations 4. la) Gill, T. P ; Mann. K R. lnorg Chom. 1980,19,30073110. (b) Gill, T P;Mann, K
the 18-electronrule R. J . Organomrt Chem. 1881,216.6S71.
the analysis of possible ligands in the system 5. Adamsan, A. W ;Fleischer, P. D . Conqta ofInagonir Photoehemistry;Wiley: New
York. 1975.
.the assumption that the anionic Cp- ligand is mare tightly 6. Wrighton. M. S., E d . A d ~ d c e in
s Chemistry &ties, 168: he.Chem. Sar.: Washing-
bound than a neutral toluene ligand tonD.C., 1978.
7. Porter. G. B. J Chem Educ lS88,60,78S790.
The Mechanism 8. Faulkner, L. R. J. Chem. Educ 1883.60,26>261.
9. Evan% D. H.; O'Connell. K. M.; Peteram,R. A.; Kelly, M. J. J Chom E h . 1885.MI,
290-293.
10. Mabbatt, G . A J Chem Educ 1889.60.691-702.
11. Kiss-, P. T: H e i n e m , W R. J. Chem. E d v r 1988,60,102706.
12.Boyd.D.C.: Bohling,D.A.:Mann,K.R.J Am. Chem. Soe IS&, 107,1611-1M4
13.Hamon.J.R:Astlue, D.:Miehand,P J.Am. Chem.Sar. 1881,103.7Sb766.

Volume 69 Number 12 December 1992 A319