Oxygen atom transfer reactions to metal carbonyls: Kinetics and mechanism of CO substitution reactions of M2(CO)9L (M=Re, L=PPh 3, PMePh2, PMe2Ph, C5H5N, or M=Mn, L=C5H5N) in the presence of (CH 3)3NO

Article abstract of DOI:10.1081/SIM-120039265

Rates for the reactions of M₂(CO)₉L (M = Re, L = PPh₃, PMePh₂, PMe₂Ph, C₅H ₅N or M = Mn, L = C₅H₅N) with L in the presence of (CH₃)₃NO as O-atom transfer reagent and CHCl ₃ as solvent are reported. The reaction rates suggest a pathway of association (k₂). The reaction rate order of Re₂(CO) ₉L with the four ligands is as follows: PPh₃ > PMePh₂ > PMe₂Ph > C₅H₅N.

Full text of DOI:10.1081/SIM-120039265

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Oxygen Atom Transfer Reactions to Metal Carbonyls:
Kinetics and Mechanism of CO Substitution Reactions
of M2(CO)9L (M = Re, L = PPh3, PMePh2, PMe2Ph,
C5H5N, or M = Mn, L = C5H5N) in the Presence of
(CH3)3NO
Li Peng a & Yi‐Ci Gao a
a College of Chemistry and Chemical Engineering , Lanzhou University , Gansu, 730000,
China
Published online: 16 Nov 2010.
To cite this article: Li Peng & Yi‐Ci Gao (2004) Oxygen Atom Transfer Reactions to Metal Carbonyls: Kinetics and
Mechanism of CO Substitution Reactions of M2(CO)9L (M = Re, L = PPh3, PMePh2, PMe2Ph, C5H5N, or M = Mn, L = C5H5N)
in the Presence of (CH3)3NO, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 34:7, 1181-1190, DOI:
10.1081/SIM-120039265
To link to this article: http://dx.doi.org/10.1081/SIM-120039265
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 34, No. 7, pp. 1181–1190, 2004
Oxygen Atom Transfer Reactions to Metal
Carbonyls: Kinetics and Mechanism of CO
Substitution Reactions of M2(CO)9L
(M5Re, L5PPh3, PMePh2, PMe2Ph,
C5H5N, or M5Mn, L5C5H5N) in
the Presence of (CH3)3NO
*
Li Peng and Yi-Ci Gao
College of Chemistry and Chemical Engineering, Lanzhou University,
Gansu, China
ABSTRACT
Rates for the reactions of M2(CO)9L (M ¼ Re, L ¼ PPh3, PMePh2,
PMe2Ph, C5H5N or M ¼ Mn, L ¼ C5H5N) with L in the presence of
(CH3)3NO as O-atom transfer reagent and CHCl3 as solvent are reported.
The reaction rates suggest a pathway of association (k2). The reaction
rate order of Re2(CO)9L with the four ligands is as follows: PPh3 .
PMePh2 . PMe2Ph . C5H5N.
Key Words: Manganese; Rhenium; Metal carbonyls; Oxygen atom
transfer; Amine N-oxide.
*
Correspondence: Li Peng, College of Chemistry and Chemical Engineering, Lanzhou
University, Gansu 730000, China; E-mail: penglii@hotmail.com.
1181
DOI: 10.1081/SIM-120039265
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Peng and Gao
INTRODUCTION
Hieber and Lipp[1] first reported the use of pyridine N-oxide to facilitate CO
release from Fe(CO)5. Since that time, such reactions have played an important
role in organometallic chemistry, particularly in the syntheses of metal carbonyl
derivatives.[2,3] The conditions for these reactions are very mild, usually pro-
ceeding at room temperature. In 1975, Shvo and Hazum[4] presented a con-
venient and effective approach for the syntheses of olefin derivatives of metal
carbonyls by using amine N-oxide. In spite of the extensive applications of
these reactions, the first detailed kinetic study of the reaction was only reported[5]
in 1987. The reaction mechanism seems to involve attack of an oxygen atom
transfer reagent to a CO group of the metal carbonyls. This results in the conver-
sion of a good ligand (CO) into a poor ligand (CO2) and formation of an
active, coordinative unsaturated intermediate, which then readily reacts with
an added-entering ligand to afford the expected substituted product.
Earlier kinetics studies of O-atom transfer reactions have been made on
[5]
mononuclear metal carbonyls M(CO)6 (M ¼ Cr, Mo, W), with the rates of
reaction increasing in the order Cr , Mo , W, whereas for metal carbonyl clus-
[6]
ters such as M3(CO)12 and M3(CO)11L[7] (M ¼ Fe, Ru, Os), the rates vary
in the opposite order Fe . Ru . Os. Suggestions were made that for the Cr-
molecular triad the order of reactivity is attributed to steric factors, but for the
Fe-cluster triad the order of reactivity decreases with the tendency to form
bridging carbonyl groups in the transition state for the reaction. Usually, one
thinks that a bridging carbonyl attracts electrons more strongly than a terminal
carbonyl; therefore, it can disperse and accept more negative electric charge
from the oxygen atom transfer reagent and stabilize the intermediate better.
Binuclear metal complexes represent the simplest class of cluster com-
plexes. Our previous investigation on the kinetics for reaction of M2(CO)10
with PPh3 or C5H5N in the presence of (CH3)3NO shows that the rates of
the reaction vary in the order Mn . Re.[8] This result is in accord with the
above metal carbonyl clusters. For the purpose of getting more information
about the presumed effect on the rates of reaction due to CO bridging, it
was decided to investigate the second substitution reactions of M2(CO)9L,
and this paper reports the kinetic data of the O-atom transfer reactions of
M2(CO)9L with different entering ligands L.
RESULTS AND DISCUSSION
Rates for the reaction of Eq. (1) of M2(CO)9L in CHCl3 with an entering
ligand (M ¼ Re, L ¼ PPh3, PMePh2, PMe2Ph, C5H5N or M ¼ Mn, L ¼
C5H5N) in the presence of (CH3)3NO were monitored by following changes

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CO Substitution Reactions of M2(CO)9L
1183
in the IR spectra (or UV-Visible absorption spectra) in the 2120–1880 cm21
range with time.
M2ðCOÞ9L þ ðCH3Þ3NO þ L ꢀ! M2ðCOÞ8L2 þ ðCH3Þ3N þ CO2
ðM ¼ Re; L ¼ PPh3; PMePh2; PMe2Ph; C5H5N or M ¼ Mn;
L ¼ C5H5NÞ
(1)
The reactants M2(CO)9L were generated by reactions of M2(CO)10 with
the entering ligand L in the presence of (CH3)3NO, and studied in situ. All
spectral changes for two typical reaction examples display good isosbestic
points (Figs. 1 and 2), which suggest stoichiometric reactions yielding disub-
stituted products.
This was confirmed by the fact that the IR spectra of the reactants and
products in the CO stretching region (Table 1) are in good agreement with
data reported[9–11] for the known compounds.
Plots of 2ln A (where A represents the value of absorbance) vs. time for
the reaction of Eq. (1) were linear over 2–3 half-lives. As is well known,
carbonyls are very sensitive to air and easily undergo changes in longer reac-
tion time reactions. Thus, longer reaction times are not necessarily suitable in
this case. They may even provide flawed results, especially, for the second
substitution reactions of the carbonyls. The validity of the kinetic data is
not only dependent on the experimental methods (such as UV, IR, or
Figure 1. IR absorbance changes of n(CO) vs. time for the reaction Mn2(CO)9-
(C5H5N) þ (CH3)3NO þ C5H5N ! Mn2(CO)8(C5H5N)2 þ (CH3)3N þ CO2 in CHCl3
at room temperature.

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Peng and Gao
Figure 2. UV-VIS absorbance changes vs. time for the reaction Re2(CO)9
(PMe2Ph) þ (CH3)3NO þ PMe2Ph ! Re2(CO)8(PMe2Ph)2 þ (CH3)3N þ CO2 in CHCl3
at room temperature.
NMR), but is also dependent on reaction rates. Many reports[5–8,12,13] show
that kinetic data of 2–3 half-live reactions are reliable, as concluded by Basolo
and his group.[14,15] We also calculated the half-lives for some of the reactions
in this communication. For the fastest reaction, the reaction of rhenium carbo-
nyl with the ligand PPh3, the half-life is only about 19 min, and the actual reac-
tion time for which data were collected was about 5 half-lives; however, the
rate is only linear over 2–3 half-lives. The same procedure has been adopted
by the authors of the above-cited references.
Table 1. The CO stretching frequencies of M2(CO)102nLn (M ¼ Mn, Re; n ¼ 1, 2).
Complex
n(CO) (cm21
)
Mn2(CO)9(C5H5N)[9]
2,089 w, 2,016 s, 2,005 m, 1,980 vs, 1,962 m, 1,943 m
2,035 s, 1,954 vs, 1,917 m
[9]
Mn2(CO)8(C5H5N)2
Re2(CO)9(PPh3)[10]
[10]
Re2(CO)8(PPh3)2
2,113 w, 2,040 w, 1,998 vs, 1,964 (sh), 1,940 m
2,000 (sh), 1,958 vs
Re2(CO)9(PMePh2)[10]
2,111 w, 2,040 w, 1,995 vs, 1,962 (sh), 1,938 m
2,015 w, 1,954 vs
[10]
Re2(CO)8(PMePh2)2
Re2(CO)9(PMe2Ph)[10]
2,108 w, 2,038 m, 1,990 vs, 1,960 (sh), 1,932 m
2,010 w, 1,949 vs
[10]
Re2(CO)8(PMe2Ph)2
Re2(CO)9(C5H5N)[11]
[11]
Re2(CO)8(C5H5N)2
2,099 w, 2,039 m, 2,011 s, 1,985 vs, 1,960 m
2,006 w, 1,950 vs, 1,917 m

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CO Substitution Reactions of M2(CO)9L
1185
The reaction rates are zero-order in PPh3 concentration (Table 2), and the
same rates are obtained for corresponding reactions of this type using other
entering ligands.
The plots of kobsd vs. the (CH3)3NO concentration show a first-order
dependence on the trimethylamine N-oxide concentration (Fig. 3). Thus,
CO substitution obeys the second-order rate law given by Eq. (2), and the
second-order rate constants for the reaction of Eq. (1) are given in Table 3.
d½M2ðCOÞ9Lꢁ
0
ꢀ
¼ k2½M2ðCOÞ9Lꢁ½ðCH3Þ3NOꢁ½Lꢁ
ð2Þ
dt
This rate law and kinetic behavior are the same as those reported earlier
for the corresponding reactions of mononuclear metal carbonyls and metal
cluster,[5–8,12] suggesting that the same associative mechanism is involved
for these second substitution reactions, where both bond making by attack
of the (CH3)3NO nucleophile and bond breaking of the M–C bond contribute
to the energetics of the rate-determining step, which is supported by the experi-
mental activation parameters: lower DH= and negative DS=.[5–8,12] This then
permits the oxidation of a CO group to the poor ligand and good leaving group
CO2, resulting in the formation of the active, coordinative unsaturated inter-
mediate “M2(CO)8L,” which then rapidly reacts with an entering ligand to
give the product M2(CO)8L2 (scheme in Fig. 4).
The second substitution reaction rates of M2(CO)9L were slower than the
first substitute reaction rates of M2(CO)10 (Table 4). This is so because the
substituted ligand L is a stronger s donor and a weaker p acceptor than a
CO group. When L substitutes a carbonyl, the positive charges on the other
carbonyl carbons decrease, which makes the nucleophilic attack slower. The
IR spectra of all reaction products show that the second substitutions occur
on the unsubstituted metal, which is in good agreement with earlier
reports.[9–11]
Previous studies[9,10] suggest that the ease of nucleophilic attack on the
carbon of a metal carbonyl correlates with the C–O stretching frequencies of the
carbonyl. The higher the value of n(CO), the greater the ease of attack on the
Table 2. Observed rate constants for the reaction of Re2(CO)9PPh3
with PPh3 of Eq. (1) in CHCl3.
T (8C)
[(CH3)3NO] (mol L21
)
[PPh3] (mol L21
)
kobsd (sec21
)
44.0
5.20 ꢂ 1023
1.58 ꢂ 1023
4.75 ꢂ 1023
7.92 ꢂ 1023
11.08 ꢂ 1023
1.14 ꢂ 1023
1.06 ꢂ 1023
1.07 ꢂ 1023
1.06 ꢂ 1023

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1186
Peng and Gao
Figure 3. Plots of kobsd vs. (CH3)3NO concentration for the reaction of Eq. (1) in
CHCl3 at 44.0 8C (M ¼ Re; 1, PPh3; 2, PMePh2; 3, PMe2Ph; 4, C5H5N).
more positive carbon that results from less p back-bonding from the metal.
The experimental results show that the rates of reaction of Re2(CO)9L decrease
in the order PPh3 . PMePh2 . PMe2Ph . C5H5N, which is in accord with the
consequence of their IR values of n(CO) and consistent with what was observed
in M3(CO)11L[7] and M4(CO)11L.[13] It is noteworthy that Re2(CO)9PPh3,
Re2(CO)9(PMePh2), and Re2(CO)9(PMe2Ph) in CHCl3 have nearly the same
n(CO) values. These similar values of n(CO) suggest that the respective carbon
atoms have similar charges, and they should respond to nucleophilic attack on
CO group based on the ground state at about the same rate, but the reaction rate
Table 3. Second-order rate constants for the reaction of Eq. (1) in
CHCl3 at 44.0 8C.
a
k2
M2(CO)9L
Re2(CO)9L
L
[mol (L sec)21
]
PPh3
1.28 ꢂ 1021
3.27 ꢂ 1022
3.36 ꢂ 1022
2.15 ꢂ 1022
PMePh2
PMe2Ph
C5H5N
Mn2(CO)9L
C5H5N
3.52 ꢂ 1022
aAt fixed concentrations of the ligand, plots of kobsd vs.
[(CH3)3NO] provide the second-order rate constant k2 at the
fixed temperature.

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CO Substitution Reactions of M2(CO)9L
1187
Figure 4. The proposed scheme for the associative mechanism of the second substi-
tution reactions of Eq. (1).
of PPh3 is greater than that of PMePh2 and PMe2Ph. An earlier investi-
gation[16] of the reaction of Fe(CO)4L complexes with PhCH2MgBr showed
that the rates of nucleophilic attack on CO group by the benzyl nucleophile
are controlled by electronic factors. The electronic character of L controls the
amount of electron density transferred to the carbonyls by Fe ! CO p back-
bonding. As the amount of back-bonding increases, the electron density on
the carbon atoms increase, and the carbon atoms become less susceptible to
nucleophilic attack. The addition of electron donating methyl groups, not only
increased electron density on the phosphorous atom of L, but also decreased
the p-p conjugation ability inner phosphorous atom and benzene ring, and
the ability to disperse and accept the increasing negative charges in the
intermediates. As the electron density can be transferred through the chemical
bonds between the L–M–M–CO groups of the clusters,[7] this also increases
the negative charges on the CO group sitting on the unsubstituted metal, which
results in a decrease of stability of the coordinative unsaturated intermediates
and makes the rates of the reaction slower.
Table 4. Second-order rate constants for the first-substitution reac-
tions and the second-substitution reactions of the binuclear metal
carbonyls with (CH3)3NO and an entering ligand L in CHCl3 at 44.08C.
k2
Complex
L
[mol (L sec)21
]
[8]
Mn2(CO)10
[8]
Re2(CO)10
PPh3
PPh3
1.73
1.11
Re2(CO)9PPh3
Re2(CO)9(C5H5N)
Mn2(CO)9(C5H5N)
PPh3
C5H5N
C5H5N
0.128
0.022
0.035

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Peng and Gao
EXPERIMENTAL
Materials and Methods
Mn2(CO)10, PMePh2, and PMe2Ph were purchased from Strem Chemicals
Co., and Re2(CO)10 was obtained from Aldrich. Trimethylamine N-oxide,
(CH3)3NO was synthesized by a literature method[17] and purified by sublim-
ation in our laboratory. CHCl3 was dried over P2O5 and distilled under N2
atmosphere before use. PPh3 was purified by recrystallization from anhydrous
ethanol. C5H5N (Strem) was distilled over CaH2 under N2 atmosphere
before use.
Instrumentation
Infrared spectra were recorded on a Nicolet-5DX FT-IR spectropho-
tometer. UV-Visible measurements were done on a Shimadzu UV-240
spectrophotometer. Constant temperature was maintained by the internal
circulating bath of the Shimadzu UV-240 in the range +0.2 8C.
Kinetic Measurements
The reactions were detected on a Nicolet 5-DX Fourier transfer infrared
spectrometer. Kinetic data were obtained by monitoring both the UV-Visible
and IR spectral changes. All reactions were carried out using oxygen-free
CHCl3 solutions. Phosphine and (CH3)3NO concentrations were at least
10 times greater than that of M2(CO)9L for pseudo-first-order conditions. In
a typical experiment, a solution (ꢀ3 mL) of (CH3)3NO and the appropriate
nucleophile L (ꢀ5 ꢂ 1023 M) in CHCl3 was mixed in a measuring flask pre-
viously filled with N2. After 15 min of temperature equilibration, a solution of
M2(CO)10 (ꢀ3 ꢂ 1024 M) in CHCl3 was syringed into the flask, which
was shaken vigorously, and then the liquid was introduced into special
temperature-constant IR cells and sealed with rubber septa. The resulting
spectral changes were monitored, and the products were characterized by
their IR spectra. Plots of 2ln A vs. time for the disappearance of reactant
and plots of ln(At 2 A1), where At represents the value of absorbance at differ-
ent times t and A1 represents the value of absorbance when the reaction is
over, vs. time for the appearance of product were linear over 2–3 half-lives
(linear correlation coefficients .0.995). The slopes of these lines gave kobsd
values. Both methods for monitoring the reaction rates yielded similar kobsd
values for a given reaction.

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CO Substitution Reactions of M2(CO)9L
1189
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Received July 8, 2003
Accepted March 7, 2004
Referee I: C. A. L. Mahaffy
Referee II: K. P. Gable

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