626

Kinetics and mechanism of dealkylation of

coordinated isocyanide in Fe(PMe3)2(t-BuNC)31
Christine L. Tennent and William D. Jones

Abstract: The zerovalent iron complex Fe(PMe3)2(t-BuNC)3 undergoes thermal cleavage of the C—N bond to give
Fe(PMe3)2(t-BuNC)2(H)(CN) and isobutylene. The reaction follows first order kinetics, and addition of the hydrogen-
atom donor 1,4-cyclohexadiene leads to the preferential formation of isobutane rather than isobutylene. Mechanistic
studies are consistent with a rate determining homolysis of the C—N bond, giving rise to tert-butyl radicals.
Key words: iron, isocyanide, elimination, C—N cleavage.

Résumé : Le complexe ferrique zérovalent, Fe(PMe3)2(t-BuNC)3, subit un clivage thermique de la liaison C—N et gé-
nère le Fe(PMe3)2(t-BuNC)2(H)(CN) et l’isobutylène. La réaction suit une cinétique du premier ordre, et l’addition du
cyclohexadiène-1,4 comme source d’hydrogène mène à la formation préférentielle de l’isobutane plutôt que
l’isobutylene. Les modèles mécanistes sont conformes à l’homolyse cinétiquement déterminante de la liaison C—N me-
nant à la formation de radicaux de tert-butyl.
Mots clés : fer, isocyanure, élimination, clivage de la liaison C—N.

Tennent and Jones 633

Introduction the complexes were found to be moderately thermally stable

at room temperature. Stability was found to decrease in the
Rathke and Muetterties (1) and Klein and co-workers (2), sequence 2,6-xylyl > Ph > CH2CMe3 > t-Bu > Me > > i-Pr >
in independent studies, reported the synthesis of the complex Et. The reaction of the isocyanides where R = i-Pr and Et
[Fe(PMe3)4], which was found to be in equilibrium with the did not give an isolable crystalline product. The complex
intramolecular oxidative addition adduct Fe(η2-PMe2CH2)- Fe(PMe3)2(t-BuNC)3 could be isolated as a yellow crystal-
(PMe3)3H. The reaction of this complex with σ-donor lig- line solid, but was found to decompose at 25 °C over several
ands and oxidative addition substrates gave evidence of this days.
facile equilibrium (3). The preparation and structural exami- All of these complexes have similar 1H NMR spectra with
nation of a series of low-valent iron phosphine isocyanide resonances for three equivalent isocyanide ligands and a
complexes using the above mentioned reactive iron species pseudotriplet (5) for the two equivalent trimethylphosphine
has been reported by our laboratory by the reaction of this ligands. This suggests a trigonal-bipyramidal geometry,
reactive species with a variety of isocyanides (eq. [1]) (4). which was confirmed by X-ray crystallography for R =
This article addresses the C—N cleavage reaction that is CH2CMe3, Ph, and 2,6-xylyl. An interesting observation is
seen in one of these derivatives, Fe(PMe3)2(t-BuNC)3 (1). the severe bending of the C-N-C linkage in each of these
complexes (Table 1). The general tendancy is for two of the
[Fe(PMe3)4] isocyanides to display a higher degree of bending than the
third. In the case of phenyl isocyanide, crystal packing
[1] forces one isocyanide ligand to be crystallographically linear
Me3P PMe3 and the remaining two ligands must then take up the excess
H
3.5 equiv. RNC metal electron density by π-back-bonding, resulting in the
Me3P Fe CH2 Fe CNR bent C-N-C. The other isocyanide complexes listed in Ta-
Me3P CNR RNC ble 1 also show this pattern. The trimethylphosphine ligands
Me2P PMe3
always occupy the axial positions.
R = Me, Et, i-Pr, t-Bu, CH2CMe3, Ph, 2,6-xylyl Benzene solutions of the Fe(PMe3)2(CNR)3 complexes,
when treated with the corresponding free isocyanide at
Several isocyanides were used, and all of the resulting 25 °C, were found to be in equilibrium with their mono- and
complexes were found to be extremely air sensitive. Most of disubstituted complexes (eq. [2]). The equilibrium constants

Received 15 September 2004. Published on the NRC Research Press Web site at http://canjchem.nrc.ca on 7 June 2005.
Submitted for publication in a special issue to honour the career contributions of Professor Howard Alper.
C.L. Tennent and W.D. Jones.2 Department of Chemistry, University of Rochester, Rochester, NY 14627 USA.
1
This article is part of a Special Issue dedicated to Professor Howard Alper.
2
Corresponding author (e-mail: jones@chem.rochester.edu).

Can. J. Chem. 83: 626–633 (2005) doi: 10.1139/V05-023 © 2005 NRC Canada
Tennent and Jones 627

Table 1. C-N-C bond angles in iron isocyanide complexes (4). Scheme 1. Mechanism for isocyanide insertion.
Molecule Angle C-N-C (°) PMe3

Fe(PMe3)2(CNCH2CMe3)3 140, 146, 166 RNC

Fe CNR
Fe(PMe3)2(CNPh)3 131.8, 131.8, 180 RNC
Fe(PMe3)2(CN-2,6-xylyl)3 147.7, 149.8, 161.3 PMe3
Fe(PMe3)(CN-2,6-xylyl)4 174.5, 167.9, 166.7, 145.1 NR
hν, -CNR
H
were found by comparison of the 1H NMR integrations of CNR C 6H 6
the free and coordinated isocyanide and PMe3 resonances. Me3P Fe PMe3
For R = tert-butyl, K1 = 0.035(5) and K2 = 0.0079(24). The RNC
equilibria for the other isocyanides were similar.

K1 Me3P
Me3P H
H NR
+CNR
Fe(PMe3)2(CNR)3 Fe(PMe3)(CNR)4 RNC Fe C6H5
[2] RNC Fe
-PMe3 RNC
+CNR RNC Ph Me2P
K2 Me2P
-PMe3
PMe3
Fe(CNR)5 NR
H
Fe
Irridation of a benzene solution of Fe(PMe3)2- RNC Ph
(CNCH2CMe3)3 in the presence of excess PMe3 resulted in RNC PMe3
the formation of a new species assigned the formula
Fe(PMe3)4(CNCH2CMe3) based on the 1H NMR spectrum 44 Hz, 1H). In a reaction run at room temperature over sev-
and the couplings observed (eq. [3]). All PMe3 ligands were eral months, only cis-2 was seen. Heating the solution to
equivalent, suggesting the d 8 complex is fluxional. 60 °C led to an equilibration with trans-2, indicating that
cis-2 is the initial kinetic product of the reaction. The reac-
hν tion is quantitative as judged by 1H NMR spectroscopy.
[3] Fe(PMe3)2(CNR)3 Fe(PMe3)4(CNR)
PMe3 Me3P
H
R = CH2CMe3 PMe3 t-BuNC Fe CN
t-BuNC t-BuNC
Fe CN-t-Bu Me2P 2
Dilute benzene solutions of Fe(PMe3)2(CNCH2CMe3)3 [4]
t-BuNC 10 : 1, cis : trans
upon irradiation gave the isocyanide insertion product, PMe3
aldimine PhCH=NCH2CMe3, and Fe(PMe3)3(CNCH2CMe3)2 Me
1
(6). The reaction was found to be catalytic in iron when low + CH2
concentrations of isocyanide are present. The two photo- Me
chemical reactions of the neopentylisocyanide complex sug-
gest the photochemical labilization of the isocyanide ligand. It has been observed that at room temperature in the solid
The proposed mechanism for the isocyanide insertion is state, 1 will also react thermally to give 2. After several
shown in Scheme 1. months, approximately 10% of 2 had formed. Analysis for
isobutylene was not done. If the material is kept at low tem-
Results peratures (<20 °C), no significant formation of 2 is ob-
served.
Thermal reaction of Fe(PMe3)2(t-BuNC)3
A benzene-d6 solution of Fe(PMe3)2(t-BuNC)3 (1), upon Kinetics of the reaction of Fe(PMe3)2(t-BuNC)3
heating at 60 °C for 24 h, showed a gradual bleaching of its UV–vis spectroscopy was found to be a convenient
yellow color accompanied by a change in the 1H NMR spec- method for determining the rate of the isocyanide cleavage
trum. A decrease of the resonances of 1 at δ 1.26 (s, 27H) reaction. The UV–vis spectrum of 1 had two broad but well
and 1.55 (pseudo t, J = 4 Hz, 18H) was observed, while new defined maxima at 309 and 390 nm, which, upon thermolysis
resonances for Fe(PMe3)2(t-BuNC)2(H)(CN) (2) as well as (formation of 2), decrease to baseline. The band at 390 nm
free isobutylene (δ 4.73, m, 1H; 1.58, m, 6H) appeared was used for kinetic studies, as it was farthest from the large
(eq. [4]). Cis and trans isomers of 2 are observed in a 10:1 solvent absorption.
ratio. The ratio is invariant over time. The resonances for the The effect of concentration of 1 on the rate of the reaction
cis isomer appear at δ 1.51 (pseudo t, J = 4 Hz, 18H), 1.10 was examined in the range of 1 × 10–4 – 9 × 10–4 mol/L, as
(s, 9H), 0.97 (s, 9H), and –10.6 (t, J = 56 Hz, 1H) while the indicated in Table 2. The rate constant was found to be inde-
resonances for the trans isomer are observed at δ 1.48 pendent of [1], although a rather large variation (10%) in
(pseudo t, J = 4 Hz, 18H), 1.06 (s, 18H), and –13.8 (t, J = kobs was observed (kobs = 4.2 (0.4) × 10–5 s–1).

© 2005 NRC Canada

628 Can. J. Chem. Vol. 83, 2005

Table 2. Kinetics data for elimination of isobutylene from 1 at Fig. 1. Eyring plot for the elimination of isobutylene from
67 °C. Fe(PMe3)2(t-BuNC)3.
[1] (mmol/L) [PMe3] (mol/L) Solvent kobs × 105 (s–1)
0.11 0 Iso-octane 4.7(0.03)
0.20 0 Iso-octane 5.1(0.02)
0.25 0 Iso-octane 3.9(0.01)
0.42 0 Iso-octane 4.6(0.007)
0.56 0 Iso-octane 4.2(0.009)
0.57 0 Iso-octane 3.7(0.004)
0.63 0 Iso-octane 4.8(0.004)
0.67 0 Iso-octane 3.8(0.005)
0.68 0 Iso-octane 3.7(0.003)
0.69 0 Iso-octane 4.4(0.002)
0.70 0 Iso-octane 4.0(0.003)
0.72 0 Iso-octane 3.9(0.002)
0.76 0 Iso-octane 4.7(0.008)
0.77 0 Iso-octane 4.2(0.009)
0.82 0 Iso-octane 3.7(0.004)
0.91 0 Iso-octane 4.5(0.02)
1.4 0.014 Iso-octane 4.2(0.2)* Table 3. Radical trap data for elimination of isobutylene from 1.
1.2 0.03 Iso-octane 4.7(0.1)*
[1,4-Cyclohexadiene] Isobutane/
1.2 0.06 Iso-octane 4.9(0.1)*
(mol/L) Solvent isobutylene
1.1 0.11 Iso-octane 4.9(0.2)*
0.97 0.97 Iso-octane 4.9(0.2)* 0.2 Benzene 0.75
0.55 0 Iso-octane 4.2(4)* 0.3 Benzene 1.04
0.43 0 Benzene 10.7(0.01) 0.3 Benzene 0.51
0.91 0 THF 10.7(0.02) 0.4 Benzene 0.80
0.98 0 DMSO 30.6(0.10) 0.4 Benzene 0.80
0.6 Benzene 1.32
Note: * = standard deviation for multiple runs. All others are first order
fits for single determination. 0.6 Benzene 0.82
0.6 Benzene 0.89
0.7 Benzene 0.96
The rate of the reaction was measured for temperatures 2.0 Benzene 3.54
ranging from 50 to 85 °C. An Eyring plot of these results 2.0 Benzene 3.17
gave ∆H‡ = 26(1) kcal/mol and ∆S‡ = 15(3) eu (Fig. 1). The 10.6 1,4-Cyclohexadiene 3.54
value of 26(1) kcal/mol for the bond breakage of the C—N
bond of coordinated isocyanide is not surprising considering
the high stability of the -CN ligand that remains intact. eral trend can be noted. As the amount of added 1,4-
The rate of isobutylene elimination was examined in both cyclohexadiene was increased, more isobutane was produced
low polarity (iso-octane) and high polarity (DMSO) sol- relative to isobutylene.
vents. The same reaction products were observed in each In an attempt to determine if a solvent cage reaction was
solvent. The resulting kobs were found to be 4.2 × 10–5 and occurring, a sample was made in neat 1,4-cyclohexadiene.
30.6 × 10–5 s–1, respectively, indicating only a small solvent Samples of 1 in benzene or neat 1,4-cyclohexadiene were
effect (7×) on the rate of the reaction. made as described in the Experimental section. The volatiles
The effect of added PMe3 on the rate of the reaction was from the samples after heating for 14 h at 67 °C were exam-
also examined. Solutions of 1 containing trimethylphosphine ined by 1H NMR spectroscopy. The benzene samples showed
in concentrations ranging from 0 to 0.97 mol/L were em- the trend previously observed; that is, an increase in
ployed. The rates of disappearance of 1 were found to be [1,4-cyclohexadiene] gave a decrease in the amount of iso-
comparable, within experimental error (Table 2). One inter- butylene produced. However, the sample made in neat 1,4-
esting observation was that additions of small amounts of cyclohexadiene gave approximately 25% isobutylene (see
trimethylphosphine to the reaction resulted in smaller stan- Table 3).
dard deviations in the kobs than found using no trimethyl- The partially labeled compound Fe(PMe3)2[CNC(CH3)-
phosphine. (CD3)2]3 was synthesized to measure the kinetic isotope
Several benzene-d6 solutions of 1 were made with varying effect of C—H vs. C—D elimination. Benzene solutions
amounts of the radical trap 1,4-cyclohexadiene. The samples containing Fe(PMe3)2(t-BuNC-d6)3 were heated for 24 h at
were examined by 1H NMR spectroscopy after heating at 67 °C in resealable NMR tubes. The reaction was complete
67 °C for 24 h, showing the formation of both isobutylene after 24 h. The volatiles from the samples were then ana-
and isobutane, plus benzene and 2. The ratio of isobutane to lyzed by GC–MS using low ionizing voltages to determine
isobutylene is given in Table 3 for various diene concentra- the ratio of d6 to d5 isobutylene, which was found to be
tions. Once again, the scatter in the data is large, but a gen- 0.56(0.01). The statistically corrected isotope effect kH/kD is

© 2005 NRC Canada

Tennent and Jones 629

Scheme 2. Proposed mechanisms for C—N cleavage in 1.

CH2 H
H t-BuNC Me
CMe2 Fe CN + CH2
t-BuNC
Fe CN t-BuNC Me
t-BuNC PMe3
PMe3
(b) +PMe3
-PMe3
PMe3 Me3P
PMe3 H
CH3 Me
t-BuNC (a) t-BuNC
Fe CN-t-Bu t-BuNC Fe CN + CH2
Fe CN + C CH3 +
t-BuNC Me
t-BuNC t-BuNC
H
PMe3 CH3 transfer Me2P
PMe3
1 2

(c)
PMe3 CH3 .
H
t-BuNC .
Fe CN + .C CH3 transfer

t-BuNC CH3
PMe3

Fig. 2. ESR spectrum upon addition of N-tert-butyl-α- Discussion

phenylnitrone (PBN) to a sample of 1 in benzene.

The thermal reaction of Fe(PMe3)2(t-BuNC)3 (1) gives the

products Fe(PMe3)2(t-BuNC)2(H)(CN) (2) and free isobutyl-
ene in quantitative yield. This reaction formally involves the
δ-elimination of the isocyanide C—H bond and cleavage of
the isocyanide C—N bond to produce the observed olefin
and the metal cyano hydride. Several mechanisms were con-
sidered for this elimination reaction (Scheme 2).
One could envision that thermal reaction of 1 leads to the
formation of a tert-butyl carbonium ion intermediate that
could then act as a proton donor towards the metal anion
(Scheme 2a). Precedence for this pathway exists in the liter-
ature on tert-butyl isocyanide (8). The lack of a strong de-
pendence of the rate of the reaction on solvent polarity,
however, argues against this pathway. Solvent effects on
ionic reaction rates are typically on the order of three to six
orders of magnitude difference (9). The effect on the thermal
therefore 1.12. The overall kobs for the reaction was observed reaction in this case was only a sevenfold difference.
to be approximately the same as for the nondeuterated mate- A second possible mechanism would involve intramole-
rial. cular elimination (Scheme 2b). If an intramolecular mecha-
Addition of N-tert-butyl-α-phenylnitrone (PBN) to a sam- nism were occurring during the thermal reaction of 1,
ple of 1 in benzene showed an immediate ESR signal trimethyl phosphine dissociation would be required as the
(Fig. 2). The signal intensity increased after heating, giving initial step to generate a vacant site. The unsaturation at the
a strong triplet of doublets with aH = 3 G and aN = 15 G. metal center would allow coordination of a terminal hydro-
These coupling values are reasonable for a tert-butyl radical gen of the isocyanide (agostic interaction). Olefin elimina-
coupled with PBN (eq. [5]) (7). tion and recoordination of the trimethyl phosphine would
result in 1 and isobutylene. One concern regarding this
mechanism is the strain needed to achieve the appropriate
geometry for agostic hydrogen coordination to the metal
. center. Earlier X-ray structural studies of 1 and similar iron
[5] O H O
complexes reported the C-N-C linkage to be bent (~130°). It
C N CMe3 C N CMe3 is not clear if this deviation from linearity would be suffi-
H cient to allow hydrogen coordination. The observation that
CMe3 the rate of the reaction is insensitive to added PMe3 at con-
+ Fe(PMe3)2(t-BuNC)3 centrations up to 1 mol/L argues against this pathway, al-
© 2005 NRC Canada
630
Scheme 3. Radical mechanism for C—N cleavage in 1.
Radical cage
PMe3 PMe3
CH3
t-BuNC t-BuNC . H.
Fe CN-t-Bu Fe CN +
t-BuNC t-BuNC CH3
PMe3 PMe3
1 2
75% Cage escape
PMe3
CH3
t-BuNC
. + .C
Fe CN
t-BuNC CH3
PMe3
though rate determining PMe3 loss in the first step would
give first order kinetics.
A third mechanism would involve the homolytic cleavage
of the N—C single bond in complex 1, which would result
in a 17-electron iron(I) species and a tert-butyl radical
(Scheme 2c). The tert-butyl radical would act as a good hy-
drogen atom donor to the iron(I) complex, directly giving
the cyano hydride product 2 and isobutylene.
Several lines of evidence point towards a radical mecha-
nism. First, isobutane formation from the reaction of 1 in the
presence of 1,4-cyclohexadiene reveals the intermediacy of
tert-butyl radicals. 1,4-Cyclohexadiene could act as a hydro-
gen atom donor towards both tert-butyl radicals and the 17-
electron metal complex to give isobutane and 2 (plus ben-
zene). As the concentration of the hydrogen donor increases,
the amount of isobutane also goes up since competitive reac-
tion of the tert-butyl radicals with the Fe(I) intermediate be-
comes less important (Scheme 3). The small amount of
isobutylene still observed in the presence of neat 1,4-
cyclohexadiene suggests the possibility that some reaction
occurs within the solvent cage. The limiting observation of
25% (minimum) isobutylene suggests that at least 1/4 of the
radical pairs react within the cage. Though tert-butyl radical
coupling to form isobutane and isobutylene is highly fa-
vored, none was observed. This may be because of the high
reactivity of the 17-electron iron complex, which would be
in excess after one pair of tert-butyl radicals coupled.
The appearance of an intense ESR signal when a benzene
solution of 1 was treated with excess PBN also suggests a
radical mechanism. A sample of tert-butyl isocyanide and
PBN in benzene gave no apparent ESR signal. No ESR sig-
nal was observed when a benzene solution of Fe(PMe3)2-
(CNCH2CMe3)3 and PBN was examined. This was
significant since the neopentylisocyanide complex is known
to be thermally stable and does not undergo the dealkylation
observed with 1. As a side note, the addition of the spin trap
2-methyl-2-nitrosopropane dimer to benzene solutions of 1
or Fe(PMe3)2(CNCH2CMe3)3 gave ESR signals in both
cases, though the intensity of the signal was smaller. It is
likely that these trapped radicals were formed as a result of
direct reaction of the metal complexes with the added spin
trap, which is a common problem with ESR spin traps.
Can. J. Chem. Vol. 83, 2005
Me3P
H
Me
t-BuNC
.C CH3
Fe CN + CH2
transfer t-BuNC
Me
Me2P
H.
transfer Me3P
H
t-BuNC
CH3
Fe CN
t-BuNC
Me2P
H
Me
+ Me
Me
The isotope effect measured for the hydrogen abstraction
reaction that is proposed to occur in the thermal rearrange-
ment of 1, where the hydrogen or deuterium atom is at-
tached in an equivalent place in the same molecule, is
commonly known as a competitive intramolecular isotope
effect (10). The small isotope effect observed for this reac-
tion may be due to a small zero point energy difference
between the two reactant-like transition states of this exo-
thermic reaction step (11).
The cleavage of isocyanide C—N single bonds by transi-
tion metals, while not unprecedented, is fairly rare. Lippard
and co-workers reported the dealkylation of [M(t-BuNC)7]2+
(M = Mo, W) in refluxing ethanol in low yield (12). Al-
though the fate of the tert-butyl group was not determined, it
was proposed to have formed either tert-butyl alcohol or iso-
butylene. Tschugaeff and Teearu reported the formation of
Pt(t-BuNC)2(CN)2 upon dissolving [Pt(t-BuNC)4]2+ in meth-
anol (13). Earlier work in our group also showed that coordi-
nation of t-BuNC to [Ru(dmpe)2] leads to the formation of
Ru(dmpe)2(H)(CN), Ru(dmpe)2(CN)2, isobutylene, and iso-
butane (14). In none of these cases was the mechanism ex-
amined in detail.
Conclusions
The thermal reaction of 1 to eliminate isobutylene and
form 2 has been found to proceed by the homolytic cleavage
of the N-t-Bu bond, producing a free tert-butyl radical and a
17-electron Fe(I) complex. The transfer of H· from the t-Bu
radical to the metal complex gives the observed products.
The observation of at least 25% isobutylene (based on the
amount of 2 formed) regardless of the amount of hydrogen
atom donor present suggests that a minimum of one fourth
of the radical reaction occurs in the radical cage.
Experimental
The solvents THF, DMSO, diethyl ether, tetraglyme, and
benzene were distilled from dark purple solutions of sodium
benzophenone ketyl under a nitrogen atmosphere. Iso-octane
was dried by refluxing with sodium under nitrogen for 48 h.
All compounds were handled in a Vacuum Atmospheres Dri-
© 2005 NRC Canada
Tennent and Jones
Lab. All NMR samples were made using resealable or
sealed NMR tubes that were prepared and degassed on a
high vacuum line. The UV–vis samples were run under ni-
trogen in a 1 cm path length quartz cell equipped with a Tef-
lon adaptor. The ESR samples were run in new NMR tubes
capped with septa. tert-Butyl isocyanide and 1,4-cyclohexa-
diene were purchased from Aldrich Chemical Company and
vacuum distilled before use. Trimethylphosphine was
purchased from Strem Chemical Company and used as
received. The Grignard MeMgI in diethyl ether (3 mol/L),
2-methyl-2-nitropropane dimer, and N-tert-butyl-α-phenyl-
nitrone (PBN) were purchased from Aldrich Chemical Co.
and used as received. Fe(PMe3)2(t-BuNC)3 was prepared as
previously described (4).
NMR spectra were obtained on a Bruker AMX-400 in-
strument. NMR chemical shifts are reported in units of δ vs.
residual benzene protons (δ 7.15 for 1H; 128.0 for 13C). UV–
vis spectra were obtained on an HP 8452A diode array
spectrophotometer, and kinetics data were processed using
HP 89531A MS DOS UV–vis operating software. Gas chro-
matography – mass spectrometry were obtained using an HP
5890 series II instrument equipped with a 30 m Carbowax
column at 50 °C and an ionizing voltage of 10 eV to ensure
only parent ion detection. Infrared data were obtained using
a Bruker ESP300 IR spectrometer.
Thermal reaction of Fe(PMe3)2(t-BuNC)3 (1)
A solution of Fe(PMe3)2(t-BuNC)3 in C6D6 (10 mg in
0.6 mL) was placed in a resealable NMR tube and heated at
60 °C. Periodic examination of the reaction by 1H NMR
spectroscopy for 24 h showed the disappearance of 1 and the
formation of two new products identified as cis-2 and trans-
2 in a 10:1 ratio, along with isobutylene (δ 4.72, m, 2H;
1.58, m, 6H).
Fe(PMe3)2(t-BuNC)3 (1)
1
H NMR (C6D6) δ: 1.264 (s, 27H), 1.547 (pseudo t, J =
3.7 Hz, 18H). 13C NMR (C6D6) δ: 20.69 (t, J = 12 Hz),
31.49 (s), 54.18 (s), 208.10 (t, J = 33 Hz). 31P NMR (C6D6)
δ: 42.08 (s).
Fe(PMe3)2(t-BuNC)2(H)(CN) (2)
1
H NMR (C6D6) (cis-2) δ: 1.51 (pseudo t, J = 4 Hz, 18H),
1.10 (s, 18H), –10.61 (t, J = 56 Hz, 1H); (trans-2) δ: 1.48
(pseudo t, J = 4 Hz, 18H), 1.06 (s, 18H), –13.78 (t, J =
44 Hz, 1H). 13C NMR (C6D6) (cis-2) δ: 55.03 (s), 0.88 (s),
30.64 (s), 20.81 (t, J = 12 Hz). 31P NMR (C6D6) (cis-2) δ:
29.97 (s); (trans-2) δ: 27.43 (s). Anal. calcd.: C 50.88, H
9.29, N 10.47; found: C 50.67, H 9.16, N 10.40.
Kinetics determinations
The solvent used for all UV–vis kinetics runs was dry iso-
octane, chosen because of its high boiling point and low va-
por pressure. A 1 cm quartz cuvette directly attached to a
Teflon adaptor allowed the very air sensitive samples to be
run on the bench top at a range of temperatures (50–85 °C).
All of the UV–vis samples were prepared in the drybox and
run under nitrogen. A UV–vis spectrum of 1 showed two
broad bands at 309 and 390 nm. The band at 390 nm was
used for the kinetic measurements as it was isolated from the
solvent and product absorptions. A stock solution of 1
631
(0.0114 mol/L) was prepared, and dilutions were made to
determine the molar extinction from a Beer’s law plot (ε =
2180 M–1 cm–1).
Concentration and solvent effects
Solutions of 1 from 1 × 10–4 – 9 × 10–4 mol/L were pre-
pared by the following procedure: In a drybox, approxi-
mately 0.1–1.0 mg of 1 was placed into a 1 cm quartz
cuvette and ~2 mL iso-octane was pipetted in. The resulting
solution was mixed, and the cuvette was placed in a
thermostated cell holder. Following an equilibration period
of 10 min, the kinetics were followed by monitoring the ab-
sorption at 390 nm for 20 h. The initial absorbance of each
run was used to calculate the concentration of 1 using Beer’s
law. The absorbance followed a first order decay, and the
kobs for each run was determined using the HP software.
Similar runs were made by dissolving samples of 1 in THF,
DMSO, and benzene.
Effect of excess PMe3
Samples were made from a stock solution prepared by
dissolving 15 mg of 1 into a 25 mL volumetric flask, adding
10 mL iso-octane and the appropriate amount of PMe3, and
filling to the final volume with iso-octane. Aliquots of the
stock solution were pipetted into the cell for kinetic runs,
and the stock solution was stored in a freezer between runs.
Reaction of 1 with 1,4-cyclohexadiene
A total of eight samples of 1 containing various amounts
of 1,4-cyclohexadiene in benzene were prepared as follows:
Benzene-d6 solutions containing 10 mg of 1 were placed in
resealable NMR tubes. Care was taken to add known
amounts of C6D6 solvent to each. 1,4-Cyclohexadiene was
added via syringe. The samples were degassed on the vac-
uum line, and the concentration of 1,4-cyclohexadiene was
determined by comparison of the area of the CH2 resonance
at δ 5.60 to the area of the tert-butyl resonance (δ 1.26) of 1
immediately following sample preparation. 1H NMR spectra
were recorded after heating at 67 °C for 25 h. The amount of
isobutylene formed was determined by comparing the area
of the CH2 resonance of isobutylene (δ 4.73) to the area of
the hydride resonance (δ –10.6). The reaction was complete
after 24 h of heating (~6 half-lives).
Samples were also prepared by dissolving 10 mg 1 in neat
1,4-cyclohexadiene. After heating at 67 °C for 24 h, the
volatiles were vacuum transferred to resealable NMR tubes
and examined by 1H NMR spectroscopy. The amount of iso-
butane to isobutylene was determined by comparison of the
integrated area of isobutane (δ 0.86, CH3) to isobutylene (δ
4.73, CH2).
ESR studies
A concentrated sample of 1 (15 mg) in benzene (0.3 mL)
was made in an NMR tube. An excess of N-tert-butyl-α-
phenylnitrone (~20 mg) was added, and the ESR was run
initially and after heating at 60 °C for 24 h. The signal in-
creased in intensity after heating but was otherwise un-
changed. A triplet of doublets was observed with aH = 3 G
and aN = 15 G. The same general procedure was used when
preparing the samples containing tert-butylisocyanide plus
PBN, PBN alone, Fe(PMe3)2(CNCH2CMe3)3 plus PBN, and
© 2005 NRC Canada
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Fe(PMe3)2(CNCH2CMe3)3 plus nitrone dimer using benzene
as the solvent.
Preparation of tert-butylisocyanide-d6
The preparation of tert-butylisocyanide-d6 was accom-
plished in 3 steps using known reactions. The first step was
the synthesis of tert-butanol-d6 from acetone-d6 by a Grig-
nard reaction (15). Into a 1000 mL round bottom flask fitted
with a septum and a 50 mL addition funnel was placed
3 mol/L CH3MgI in ether (220 mL, 0.66 mol) and 250 mL
of diethyl ether. The solution was cooled to 0 °C under a ni-
trogen atmosphere, and acetone-d6 (40 mL, 0.49 mol) was
slowly added to the ether solution. The flask was allowed to
warm to room temperature and was stirred overnight under
nitrogen. After 18 h, the solution was again placed in an ice
bath, and 50 mL of 10% HCl (aq) was slowly added to neu-
tralize the excess MeMgI. The solution was warmed to room
temperature, and the tert-butanol-d6 was extracted from the
aqueous layer using 3 × 50 mL aliquots of diethyl ether. The
ether was removed from the combined extracts, giving tert-
butanol-d6 (15.8 g, 0.20 mol, 35% yield). 1H NMR (C6D6) δ:
1.06 (s). Overnight reaction is required to give reasonable
yields.
The second step was the formation of tert-butylformamide-
d6 from the tert-butanol-d6 via a Ritter reaction (16). Cau-
tion must be taken in this step because of the formation of
HCN. In a 250 mL Erlenmeyer flask, tert-butanol-d6 (15.8 g,
0.20 mol) and potassium cyanide (15 g, 0.23 mol) were dis-
solved in 25 mL acetic acid. A solution of 25 mL H2SO4 and
25 mL acetic acid was added dropwise over a period of 2 h
to the solution, keeping the temperature below 60 °C. The
mixture was allowed to stir overnight at room temperature.
After 16 h, the mixture was poured into 500 mL of ice
water. The solution was placed in an ice bath, and 15% KOH
(aq) was added slowly until the acid was neutralized. The
pH was checked using litmus paper. The tert-
butylformamide-d6 was extracted using 5 × 100 mL portions
of diethyl ether. The ether was dried over potassium carbon-
ate overnight and then removed by distillation. Fractional
distillation gave tert-butylformamide-d6 (5.9 g, 0.06 mol,
30% yield). bp 200 °C. 1H NMR (C6D6) δ: 0.89 (s), 1.19 (s).
GC-MS (10 eV) m/z: 107 ([M]+), 92 ([M+ – CH3]), 89
([M+ – CD3]).
The final step was the dehydration of the formamide using
POCl3 (17). Into a 250 mL round bottom flask equipped
with a 10 mL addition funnel, condenser, and a mechanical
stirrer was placed tert-butylformamide-d6 (5.9 g, 0.06 mol),
pyridine (30 mL, 0.37 mol), and 100 mL diethyl ether. The
solution was cooled to 0 °C in an ice bath. POCl3 (7 mL,
0.09 mol) was placed into the addition funnel. After purging
with nitrogen for 10 min, the POCl3 was slowly added. Care
must be taken to ensure rapid stirring during the addition.
The solution was allowed to warm to room temperature and
then refluxed for 1 h. The flask was again placed in an ice
bath and distilled water was added to neutralize the excess
POCl3 and dissolve the salts that formed. The organic layer
was separated from the aqueous layer, and the aqueous layer
was washed with ether (5 × 50 mL). The combined organic
layers were dried over magnesium sulfate. The ether was re-
moved by distillation and tert-butylisocyanide was obtained
by vacuum distillation (0.5 mL, 0.005 mol, 8% yield). 1H
Can. J. Chem. Vol. 83, 2005
NMR (C6D6) δ: 0.87 (t, J = 4 Hz). GC-MS (10 eV) m/z: 89
([M]+), 74 ([M+ – CH3]), 71 ([M+ – CD3]), 63 ([M+ – CN]).
Preparation of Fe(PMe3)2(t-BuNC-d6)3
The synthesis was the same as described previously (4)
for the protio isocyanide complex, using FeCl2 (0.14 g), Mg
(0.08 g), and PMe3 (103 mmHg (1 mmHg = 133.322 Pa),
300 K, 1.056 L) in THF (50 mL) and adding 0.30 mL t-
BuNC-d6.
Isotope effect determinations
The determination of the isotope effect was accomplished
using three separate samples prepared in resealable NMR
tubes. A benzene solution of 20 mg Fe(PMe3)2(t-BuNC-d6)3
was heated at 67 °C for 24 h. The volatiles were vacuum
distilled from the NMR tube to a two-neck flask equipped
with an adapter and a septum. The benzene solutions were
analyzed by GC–MS using the conditions stated above to
determine the ratio of d6:d5 isobutylene. The three samples
showed ratios of 0.56 (0.01), 0.55 (0.02), and 0.56 (0.01).
Acknowledgement
The US Department of Energy, Grant FG02–86ER13569
are gratefully acknowledged for their support of this work.
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© 2005 NRC Canada