Professional Documents
Culture Documents
and Utilization
Closing the Oxygen Cycle: From Biomimetic Oxidation
to Artificial Photosynthesis
Erik Karlsson
c Erik Karlsson, Stockholm 2011
ISBN 978-91-7447-289-9
This thesis describes the development and study of catalysts for redox reac-
tions, which either utilize oxygen or hydrogen peroxide for the purpose of
selectively oxidizing organic substrates, or produce oxygen as the necessary
byproduct in the production of hydrogen by artificial photosynthesis.
The first chapter gives a general introduction about the use of environmen-
tally friendly oxidants in the field of organic synthesis, and about the field of
artificial photosynthesis.
The second chapter describes a computational study of the mechanism of
palladium-catalyzed oxidative carbohydroxylation of allene-substituted con-
jugated dienes. The proposed mechanism, which was supported by DFT cal-
culations, involves an unusual water attack on a (π -allyl)palladium complex.
The third chapter describes a computational study of the oxidation of un-
functionalized hydrocarbons, ethers and alcohols with hydrogen peroxide, cat-
alyzed by methyltrioxorhenium (MTO). The mechanism was found to proceed
via rate-limiting hydride abstraction followed by hydroxide transfer in a sin-
gle concerted, but highly asynchronous, step as shown by intrinsic reaction
coordinate (IRC) scans.
The fourth chapter describes the use of a new hybrid (hydroquinone-Schiff
base)cobalt catalyst as electron transfer mediator (ETM) in the palladium-
catalyzed aerobic carbocyclization of enallenes. Covalently linking the two
ETMs gave a fivefold rate increase compared to the use of separate compo-
nents.
The fifth chapter describes an improved synthetic route to the
(hydroquinone-Schiff base)cobalt catalysts. Preparation of the key
intermediate 5-(2,5-hydroxyphenyl)salicylaldehyde was improved by
optimization of the key Suzuki coupling and change of protecting groups
from methyl ethers to easily cleaved THP groups. The catalysts could thus be
prepared in good overall yield from inexpensive starting materials.
Finally, the sixth chapter describes the preparation and study of two cata-
lysts for water oxidation, both based on ligands containing imidazole groups,
analogous to the histidine residues present in the oxygen evolving complex
(OEC) and in many other metalloenzymes. The first, ruthenium-based, cata-
lyst was found to catalyze highly efficient water oxidation induced by visible
light. The second catalyst is, to the best of our knowledge, the first homoge-
neous manganese complex to catalyze light-driven water oxidation.
List of Publications
This thesis is based on the following papers, which are referred to in the text
by their roman numerals.
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.1 Use of Environmentally Friendly Oxidants . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.1.1 Biomimetic Oxidation Using a Coupled Catalytic System . . . . . . . . . . . 13
1.1.2 Palladium-Catalyzed Oxidative Carbocyclization of Allenes . . . . . . . . . 14
1.1.3 Methyltrioxorhenium (MTO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.2 Artificial Photosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.2.1 Water Oxidation Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.2.2 Model Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2 Mechanism of the Palladium-Catalyzed Carbohydroxylation of
Allene-Substituted Conjugated Dienes: Rationalization of the Recently
Observed Nucleophilic Attack by Water on a π -Allyl)palladium
Intermediate (Paper I) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3 Oxidation of Ethers, Alcohols and Unfunctionalized Hydrocarbons by the
Methyltrioxorhenium/H2 O2 System: A Computational Study on Catalytic
C–H Bond Activation (Paper II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.2 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.2.1 Oxidation of Alcohols and Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.2.2 Solvent Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4 Efficient Reoxidation of Palladium by a Hybrid Catalyst in Aerobic,
Palladium-Catalyzed Carbocyclization of Enallenes (Paper III) . . . . . 39
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.2 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5 Efficient Synthesis of Hybrid (Hydroquinone-Schiff base)cobalt Oxida-
tion Catalysts (Paper IV) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
5.2 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
5.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
6 Water Oxidation Catalysts Based on Imidazole-Containing Ligands (Pa-
pers V, VI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
6.2 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
6.2.1 Synthesis of Imidazole-Based Ligands . . . . . . . . . . . . . . . . . . . . . . . 49
6.2.2 Ruthenium Catalyst for Water Oxidation (Paper V) . . . . . . . . . . . . . . . 51
6.2.3 Manganese Catalyst for Water Oxidation (Paper VI) . . . . . . . . . . . . . . 52
6.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
Abbreviations
bpy 2,2’-bipyridine
BQ 1,4-benzoquinone
Co(salmdpt) bis(salicylideniminato-3-propyl)methylaminocobalt(II)
DCM dichloromethane
deeb 4,4’-bis(ethoxycarbonyl)-2,2’-bipyridine
DMDO dimethyldioxirane
HQ hydroquinone
MS mass spectrometry
MTO methyltrioxorhenium
TFA – trifluoroacetate
THF tetrahydrofuran
THP tetrahydropyranyl
UV/Vis ultraviolet-visible
1. Introduction
13
Starting material catox H2O
14
O
[Pd] [Pd]
AcO OAc
R R
OH O
[Pd] [Ru]
OAc R1 R2 R1 R2
R3 R3
[Pd] NH [Ru] N
RO OR
R1 R2 R1 R2
E E E E E E
E HO E
[Pd] [Pd]
Me Me Me Me Me Me
(E=CO2Me)
Scheme 1.3: Oxidation reactions using coupled catalytic systems, with O2 as terminal
oxidant.
cat. PdCl2
cat. CuCl2
CH2=CH2 + 1/2 O2 CH3CHO
H2O
H
H
H
+ H PdII 2 CuI 1/2 O2
H2O
O
Pd0 2 CuII H2O
H
1 mol% of Pd(TFA)2 E
E E
4 mol% of benzoquinone E
n 1 mol% of Fe(Pc) n
+ 1/2 O2 + H2O
toluene, 95 oC
R' R R
R'
(E=CO2Me) (75-96%)
15
a coupled catalytic oxidation using Pd(TFA)2 as substrate-specific catalyst,
BQ and Fe(Pc) as ETMs, and O2 as terminal oxidant (Scheme 1.6).
E E
OH
n
PdII [Fe(Pc)]ox H2O
R' R
OH
O
E
E
n Pd0 Fe(Pc) 1/2 O2
O
R
R'
(E = CO2Me)
O H2O2 O O H2O2 O O
Me Re O Me Re O Me Re O
O H2O O H2O O O
1 2 3
Nu
O Nu O O
Me Re O
O
O Nu
4
16
The nucleophile, which could be the lone pair of a heteroatom (N, P, S) or the
π -bond of an olefin, attacks one of the peroxo oxygens leading to cleavage of
the O-O bond and formation of complex 4 (Scheme 1.7). Release of product
then regenerates complex 2.
MTO is particularly useful as a catalyst for epoxidation of olefins, reported
by Herrmann in 1991. 16 Initially, an anhydrous solution of H2 O2 in tert-
butanol was used to minimize hydrolysis of the resulting epoxide, but sig-
nificant hydrolysis still occurred in many cases due to the water formed as
byproduct and the Lewis acidity of MTO. This problem could be avoided
by addition of an amine in excess, however with the expense of severely
reduced catalytic activity. 17 Later, it was reported by Sharpless that a sub-
stoichiometric amount of pyridine as cocatalyst accelerates the reaction and
also prevents hydrolysis. 18 The solvent was also changed from tert-butanol to
dichloromethane (DCM). Thus, even hydrolytically sensitive epoxides could
be obtained, even though aqueous H2 O2 was used as oxidant.
17
CH4 + H2 O −−→ 3 H2 + CO (1.1)
C + H2 O −−→ H2 + CO (1.2)
CO + H2 O −−→ H2 + CO2 (1.3)
E −◦ =1.23 V
2 H2 O −−−−−−→ 2 H2 + O2 (1.4)
Sunlight is a promising source of renewable energy, but its use has so far
been severely limited by the high costs of the currently available technology. 20
The availability of sunlight also varies greatly over the day and the year, pos-
ing serious problems for the direct generation of electricity from sunlight,
unless technology for the large-scale storage of energy is available. The prob-
lem of solar energy utilization has, however, been solved hundreds of millions
of years ago by nature, in the form of the photosynthesis occurring in plants,
algae and many species of bacteria (Eq 1.5).
hν
n CO2 + n H2 O −→ C(H2 O)n + n O2 (1.5)
hν
2 H2 O −→ 2 H2 + O2 (1.6)
Photosynthesis leads to the generation of biomass, which could be burnt for
energy, subsequently used for hydrogen production, for example by the elec-
trolysis of water. This is, unfortunately, a highly inefficient process due to the
great losses of heat at each stage. Another option is the chemical production
of hydrogen, by the means of biomass gasification, but that is also fairly inef-
ficient. Conversely, by taking inspiration from nature, instead of exploiting it,
artificial photosynthesis could be accomplished. This has been envisioned to
efficiently afford hydrogen by the direct splitting of water using solar energy
(Eq 1.6). 20
e- e-
2 H 2O H2
D P A
O2 + 4 H+ 2 H+
18
corresponding to chlorophyll in photosynthesis, transfers an electron to the
acceptor, where the electrons are used to reduce protons to hydrogen. The
photosensitizer, now in its oxidized state, then abstracts an electron from
the donor or water oxidation catalyst, corresponding to the oxygen evolving
complex (OEC) in photosystem II. After absorption of four photons, the water
oxidation catalyst has lost four electrons, enabling it to oxidize two molecules
of water to one molecule of oxygen, thus returning to its reduced state, ready
to deliver more electrons to the photosensitizer.
3+
R R
N N
4+
N N N N
N Ru Ru N
OH2 H2O Cl
N N
N N
O N N
N Ru Ru N
N N N N
R R
R = CH3, CF3, NMe2
5 6
The first homogeneous catalyst for water oxidation (5) was reported by
Meyer et al. in 1982. 22 Catalyst 5, which is based on ruthenium, was shown to
oxidize water with a turnover number (TON) of ca 13 using ceric ammonium
nitrate (CAN) as the oxidant. 23 After the initial breakthrough, however, the
progress in the field was slow for more than twenty years, until 2005 when
Thummel et al. reported a series of ruthenium-based catalysts (6) that are
able to catalyze water oxidation with greatly improved TONs of up to about
500, also using CAN as oxidant. 24 Since then, a variety of ruthenium-based
catalysts have been reported, ranging from mononuclear to multinuclear com-
plexes. 25–36 In addition, a few catalysts based on iridium 37,38 and cobalt 39,40
have been reported.
19
Despite the relatively high efficiency of the recently reported ruthenium cat-
alysts, the high cost and low natural abundance of ruthenium makes their use
in large scale applications questionable. On the contrary, manganese, which
is present in the active site of the OEC as an oxo-bridged Mn4 Ca cluster, 41 is
both inexpensive and readily available, being after iron and titanium the third
most abundant transition metal in Earth’s crust. 42 Inspired by the OEC, many
attempts have been made to develop manganese-based catalysts for water ox-
idation. Several homogeneous manganese complexes have been prepared and
studied as models of the OEC, 43–46 but none of these have so far succeeded in
oxidizing water catalytically, using a one-electron oxidant as required for ap-
plication in a system for artificial photosynthesis. Two of the most well-known
model complexes are shown in Figure 1.3. 43,44
3+ 2+
N N N O N
OH2 OH2
O N
N Mn Mn N O
N Mn Mn N
O O
H2O N H2O
N N N O N
7 8
20
Scheme 1.8: Model system using Ru(bpy)32+ as photosensitizer and S2 O82 – as electron
acceptor (WOC = water oxidation catalyst).
21
2. Mechanism of the Palladium-
Catalyzed Carbohydroxylation of
Allene-Substituted Conjugated
Dienes: Rationalization of the
Recently Observed Nucleophilic
Attack by Water on a π -Allyl)palladium
Intermediate (Paper I)
2.1 Introduction
In the previously reported palladium-catalyzed carbohydroxylation
of allene-substituted dienes, 49 allene-diene 9 reacts with water in the
presence of BQ (10) and Pd(TFA)2 to form the product 11 (Scheme 2.1).
The BQ could either be used in stoichiometric amounts, or in catalytic
amounts in combination with Fe(Pc) and O2 as terminal oxidant, in a
triple-catalytic system similar to that shown in Scheme 1.6. The reaction,
which occurs in water, is suggested to involve water attack on an intermediate
(π -allyl)palladium complex.
E E O OH
Pd(TFA)2 H E
(1 mol%) HO E
· + H2O + +
H2O/THF
(4:1) H
O OH
9 10 11 12
(E = CO2Me)
23
E E E E E E
H2O E E
Pd(TFA)2 -TFA
. .
TS13-14 Pd
H2O Pd H2O
H2O
Pd
O O H OH2
O O
9 CF3 15
CF3
13 14 TS15-16
OMe
E E E E E E E
H2O O
O BQ
E E
E E E E
HO
HO
TFA
H2O
H
Pd TS20-21 Pd
O O
11
+ Pd(II) + hydroquinone
O H2O O H2O
20 21
24
(a) Structure of complex 13. (b) Structure of transition state TS13-14 .
Figure 2.1
C3 and C4 (Figure 2.4(a)). The bond lengths to the terminal carbons Pd−C2
(2.16 Å) and Pd−C4 (2.20 Å) are similar. In the next step complex 18 should
be attacked by water to form product 11. Water is, however, too poor a nu-
cleophile to react with unactivated π -allylpalladium complexes such as 18. 50
The water attack requires the presence of BQ, which is assumed to coordinate
to palladium forming complex 19 (Figure 2.4(b)).
The terminal double bond in 19 could then coordinate to palladium form-
ing the chelated complex 20. In complex 20 the Pd−C4 distance (2.72 Å) is
significantly longer than the Pd−C2 distance (2.16 Å), suggesting a high re-
activity towards nucleophilic attack at C4. Indeed a transition state (TS20-21 ,
Figure 2.5(b)) for the attack of water on complex 20 was found with an activa-
tion energy of 10.7 kcal/mol in water with respect to 20 (Figure 2.8). Complex
21 (Figure 2.6) is then formed, which after decomplexation releases the prod-
uct 11.
The calculated energy profile for the entire reaction sequence in the gas
phase is given in Figure 2.7 and the energy profile in water, obtained from
PB-SCRF calculations of the gas phase geometries is given in Figure 2.8. The
energy profile in THF is similar to that in water. We have not calculated the
transition states for the ligand exchanges converting 14 −−→ 15, 18 −−→ 19 and
19 −−→ 20, since these transition states are supposed to be quite low and will
not change the overall energy profile.
The first two steps, allylic C−H activation (13 −−→ 15) and migratory inser-
tion (15 −−→ 16) are expected to be fast and exothermic. After that the energy
surface is essentially flat, giving an equilibrating mixture of allylpalladium
complexes 16, 17, 18, 19 and 20. The most stable species in water is 18 at
−43 kcal/mol with respect to 13, and the most stable species in the gas phase
25
(a) Structure of complex 14. (b) Structure of complex 15
Figure 2.2
2.3 Conclusions
We have found that the palladium-catalyzed reaction of allene-substituted
dienes in water proceeds via the pathway proposed in our previous
experimental work. Coordination of a carbon-carbon double bond in
the endo-(π -allyl)palladium complex 19, obtained from intramolecular
syn-carbopalladation of a 1,3-cyclohexadiene, is a highly likely intermediate
according to DFT calculations. The calculations predict the formation of
intermediate 20 which is attacked by water on the allylic carbon. The
transition state of the water attack is, according to the PB-SCRF calculations
in water, 23 kcal/mol above the most stable species 18.
26
(a) Structure of transition state TS15-16 . (b) Structure of complex 16.
Figure 2.3
Figure 2.4
Figure 2.5
27
Figure 2.6: Structure of complex 21.
20 TS13-14
9
10 14
−1
0 TS15-16
Energy (kcal/mol)
13 −10
TS20-21
-10 0
−18
28
20 TS13-14
10
14
10
3
TS15-16
0
Energy (kcal/mol)
−9
13
-10 0 TS20-21
−20
-20 15
TS16-17 TS17-18
−15 19
−33
-30 −34
−37
20
-40 −31
16 17
−37 21
-50 −38 18
−41
−43
-60
29
3. Oxidation of Ethers, Alcohols
and Unfunctionalized Hydrocarbons
by the Methyltrioxorhenium/H2O2
System: A Computational Study
on Catalytic C–H Bond Activation
(Paper II)
3.1 Introduction
Methyltrioxorhenium (MTO) has been reported to catalyze oxidation of un-
functionalized tertiary hydrocarbons to alcohols using hydrogen peroxide as
terminal oxidant. 55,56 The mechanism of this reaction is intriguing, because
hydrocarbons do not have any obvious nucleophilic site that could attack the
peroxide oxygen in MTO. It has also been shown that the reaction does not
proceed via radical intermediates. 57 Instead, based on an analogy with the ox-
idation of hydrocarbons using dimethyldioxirane (DMDO), 58 it was proposed
that the reaction proceeds via a side-on insertion of the oxygen atom into the
C−H bond (Scheme 3.1). 56 However, there is no experimental evidence for
the side-on insertion. Furthermore, it is highly unlikely due to the great steric
hindrance when a tertiary C−H bond is approached from the side.
O O O O
Me Re O Me Re O
O O O H
H O
R R
31
straction mechanism is possible, a DFT-based (B3LYP 51 /lacvp** 52,53 ) com-
putational study was performed.
O O O O O O
Me Re O Me Re O Me Re O
O O H O H
O O O
H R R
R
Figure 3.1: Optimized structures of the catalytically active species MeRe(O)(O2 )2 (3)
and MeRe(O)2 (O2 ) (2). All distances are in Å.
32
O O 2
O Re Me
OH
O O
23 H
3
CH
H
3-2
ial
TS
H 25
tor
ua
H
eq
Me
a xi
TS 3
H
al
H O O
CH
3 Re
-2
22 O H
4
O O
H 24 2 OH
25
Figure 3.2: Transition states for the oxidation of the equatorial and axial C−H bonds
of cis-1,2-dimethylcyclohexane by complex 3. All distances are in Å.
from TS3-23 are shown in Figure 3.3. The results of the IRC scan from TS3-24
are similar. The IRC scan shows that the reaction proceeds from TS3-23 to the
product complex 23 in a concerted fashion without any intermediates. Even
though the reaction is concerted, it is still highly asynchronous. First the hy-
dride is transferred from carbon to oxygen, while the electrons populate the
O−O antibonding orbital leading to cleavage of the O−O bond and forma-
tion of a Re-bound OH-group and a carbocation. The OH-group, which now
has its partially positively charged hydrogen oriented towards the carbocation,
then rotates around the Re−O bond to orient the negatively charged oxygen
towards the carbocation. The OH-group then transfers from rhenium to carbon
leading to the product complex 23. The fact that no cationic intermediate is
formed is in agreement with the observed stereospecificity of the reaction and
the absence of ether products resulting from reaction with alcoholic solvents.
For example, it has been demonstrated that oxidation of 22 in tert-butanol
as solvent affords the corresponding alcohol (25) as a single diastereoisomer
with retention of configuration in 98 % yield (Scheme 3.3). 55
For completeness, the oxidation of 22 by the monoperoxo complex 2, was
subsequently modeled. The transition state (TS2-26 ) is shown in Figure 3.4,
and the potential energy barrier is 30 kcal/mol, which is 7 kcal/mol higher
33
(a) Frame 05: 20.5 kcal/mol (b) Frame 10: 15.5 kcal/mol
(c) Frame 15: 4.1 kcal/mol (d) Frame 20: −11.5 kcal/mol
(e) Frame 25: −25.9 kcal/mol (f) Frame 30: −38.7 kcal/mol
(g) Frame 35: −50.8 kcal/mol (h) Frame 40: −60.8 kcal/mol
(i) Frame 45: −65.7 kcal/mol (j) Frame 50: −67.4 kcal/mol
Figure 3.3: Selected frames from IRC scan from the transition state TS3-23 towards
23. All distances are in Å. The OH-transfer is clearly seen starting from Frame 30
onwards.
34
Figure 3.4: Transition state (TS2-26 ) for the oxidation of the equatorial C−H bond of
cis-1,2-dimethylcyclohexane by monoperoxo complex 2. All distances are in Å.
Figure 3.5: Transition state (TS3-27 ) for the oxidation of toluene by complex 3. All
distances are in Å.
35
Figure 3.6: Transition state (TS3-28 ) for the oxidation of 1-phenylethanol by complex
3. All distances are in Å.
O O
TS3-28 Me Re O O
H OH HO OH
O H
O Ph
Ph Ph
Ph OH
29 3 30 31
28 2 H 2O
The absence of O−H bond cleavage in TS3-28 could explain why the re-
action also works with ethers. Indeed, a similar transition state (TS3-32 ) for
the oxidation of 1-phenylethyl methyl ether (33) was found (Figure 3.7), with
an activation energy of 21 kcal/mol. Analogously, the IRC scan resulted in
a hemiacetal (32), which after decomplexation and elimination of methanol
would afford the corresponding ketone (Scheme 3.5).
Figure 3.7: Transition state (TS3-32 ) for the oxidation of 1-phenylethyl methyl ether
by complex 3. All distances are in Å.
36
O O
H OMe TS3-32 Me Re O HO OMe O
O H
O Ph
Ph Ph
Ph OMe 31
33 3 34
32 2 MeOH
3.3 Conclusions
A new mechanism for the MTO-catalyzed oxidation of tertiary hydrocarbons,
alcohols, and ethers using hydrogen peroxide has been proposed and sup-
ported by DFT calculations. All reactions proceed through an initial hydride
abstraction followed by hydroxide transfer in a single concerted step without
formation of ionic intermediates, as shown by IRC scans. For tertiary hydro-
carbons, alcohols are formed directly. For alcohols and methyl ethers, hydrates
and hemiacetals are formed, respectively, which after elimination of water or
methanol afford the corresponding ketone.
37
4. Efficient Reoxidation of Palladium
by a Hybrid Catalyst in Aerobic,
Palladium-Catalyzed Carbocyclization
of Enallenes (Paper III)
4.1 Introduction
In the palladium-catalyzed aerobic carbocyclization of enallenes (Scheme 1.5,
Scheme 1.6), 6 a triple-catalytic system consisting of Pd(TFA)2 , BQ and
Fe(Pc) was used to transfer electrons from the substrate to molecular oxygen.
The reaction was, however, slow and required elevated temperature (95 ◦C).
Slow addition of the substrate was also necessary to avoid non-oxidative
side-reactions due to the inefficient electron transfer. The solvent was also
changed from THF in the original stoichiometric reaction 10 to toluene in
order to accommodate the required temperature. This is far from optimal due
to the insolubility of Pd(TFA)2 in toluene.
One way to improve the election transfer would be to covalently link BQ to
the oxygen-activating catalyst. The electron transfer then becomes intramolec-
ular instead of intermolecular. This had been done previously in the group by
linking HQ to a porphyrin. 59 Although the use of this catalyst led to improved
electron transfer it is difficult to synthesize and furthermore it is sensitive to
degradation. More recently, attempts were made to link HQ to Fe(Pc), both di-
rectly and with a tether, without any success. The problem could have been the
very limited solubility of Fe(Pc) derivatives in most solvents. Whereas Fe(Pc)
works efficiently as a heterogeneous catalyst in the aerobic oxidation of HQ,
it seems that the molecule containing the BQ moiety has to be in solution to
efficiently reoxidize the palladium catalyst.
The attention was therefore turned towards cobalt Schiff base complexes
instead, which finally led to development of the hybrid catalysts 35 and 36
(Scheme 4.1). Their synthesis and application in the palladium-catalyzed di-
acetoxylation of conjugated dienes was previously reported in a communica-
tion. 60 A preliminary study on the application of catalyst 36 in the carbocy-
clization of enallenes was also reported. Unfortunately, there were only minor
improvements compared to the triple-catalytic system. The reason is probably
that catalyst 36 has very low solubility in toluene.
While studying the reaction with stoichiometric amounts of BQ, it was dis-
covered that the presence of protic solvents, such as methanol, led to a sig-
39
OH
OH N O OH N N HO
Co Co
O N N HO O O
HO HO OH
35 36
E E Pd(OAc)2 (cat) HE E
35 or 36 (cat)
· solvent
O2 (1 atm) H
37 38
40
Table 4.1: Aerobic carbocyclization of substrate 37.
41
ethanol under O2 at 75 ◦C without any hybrid catalyst. In this reaction, none of
the oxidation product 38 was detected. Instead significant amounts of byprod-
ucts were formed showing that, for this reaction, direct reoxidation of palla-
dium(0) by O2 is not possible. Electron transfer mediators are thus required.
4.3 Conclusions
The use of hybrid catalyst 35 gives approximately a fivefold increase in re-
action rate compared to the use of separate BQ and Co(salmdpt) in ethanol.
Changing the solvent from toluene to ethanol also led to significant improve-
ments. In the absence of catalyst 35 or any other electron transfer mediations
the aerobic carbocyclization is several orders of magnitude slower and side
reactions take over. The use of catalyst 35 is thus an important complement to
the systems that are already used for reoxidation of Pd 0 by O2 . 4
42
Table 4.2: Aerobic carbocyclization of different substrates using catalyst 35.
E E HE E
1 0.8 97
H
37 38
E E E E
2 11 94
39 40
E E HE E
3 2–3 96
H
41
42
E E E E
4 2–3 94
43
44
E E HE E
5 2–3 96
H
45 46
a The reactions were carried out on a 1 mmol scale with Pd(OAc)2 (1 mol%),
hybrid catalyst 35 (1 mol%) in EtOH (2 ml) at 75 ◦C under O2 (1 atm).
b Isolated yield of pure product.
43
5. Efficient Synthesis of Hybrid
(Hydroquinone-Schiff base)cobalt
Oxidation Catalysts (Paper IV)
5.1 Introduction
Hybrid catalysts 35 and 36 were recently prepared and were found to increase
the rate of electron transfer in biomimetic oxidation reactions. 60 However, the
practical use of hybrid catalysts 35 and 36 in oxidation has been held back
by the inefficient preparation of the key intermediate 47, which is required for
their preparation (Scheme 5.1).
OH
OH
O OH
OH N OH N N HO
Co Co CHO
O N N HO O O
HO HO OH OH
35 36 47
45
N
N
OH
OH
N N
CHO NH2 NH2
51 OH HO
EtOH HO OH
OH
47 94 %
OH 53 HO
95 % Co(OAc)2
MeOH
OH
OH N O
Co
O N N HO
HO
35
Even though the route to intermediate 47 is short and seemingly easy, it has
some major drawbacks. First, the starting materials 48 and 49 are expensive.
The second drawback is the moderate yield of the Suzuki coupling. The re-
action is also producing significant amounts of byproducts, requiring lengthy
chromatographic purification. Finally, deprotection of the methyl ethers re-
quires the use of boron tribromide, which is a harsh and expensive reagent.
This leads to partial decomposition of the product, thus lowering the yield and
requiring chromatographic purification.
Therefore, we decided to develop a new synthetic route to intermediate 47.
The objectives were to use inexpensive starting materials, improve the yield
and selectivity of the Suzuki coupling and change the methyl ethers to protec-
tive groups that can be cleaved off cleanly under mild conditions, thus improv-
ing the yield and avoiding chromatographic purification in the deprotection
step.
46
OH NH2
OH
CHO NH2 OH N N HO
52
OH HO
OH EtOH
47 70 % HO OH
54
95 % Co(OAc)2
MeOH
OH N N HO
Co
O O
HO 36 OH
acetate. THP groups were chosen for protection of HQ because they can be
cleaved off easily under weakly acidic conditions.
In the next step 56 was ortho-lithiated by treatment with n-butyllithium, fol-
lowed by quenching with triisopropyl borate and hydrolysis to obtain boronic
acid 57. In this reaction the THP group promotes the ortho-lithiation by co-
ordinating to n-butyllithium. However, the purification of the boronic acid
proved to be difficult. It could be purified by silica gel chromatography, but
due to partial decomposition on the column, the recovery was low. Recrys-
tallization was not possible since the compound is an oil. Attempts were also
made to remove the THP groups prior to isolation, but that only resulted in
decomposition.
Finally, the crude boronic acid 57 was used directly in a Suzuki cross-
coupling with unprotected 5-bromosalicyladehyde (58) under phase-transfer
conditions using a catalyst formed in situ from palladium acetate and triph-
enylphosphine affording 59 in 94 % yield after column chromatography. The
major improvement arises from the change of solvent from N,N -dimethyl-
formamide (DMF) to a mixture of toluene, ethanol and water. When THP
protected boronic acid 57 was used in the original Suzuki conditions with
DMF as solvent, complex mixtures were obtained.
There were some difficulties in the deprotection of 59 due to the acid sensi-
tivity of intermediate 47. Initial attempts using p-toluenesulfonic acid resulted
in decomposition. Finally, deprotection was achieved with PPTS in ethanol-
water (9:1) at 60 ◦C. Pyridine was added prior to concentration of the reaction
mixture to avoid decomposition and reversal of the reaction. The intermediate
47
OH
CHO
5.3 Conclusions
A new synthetic route to hybrid catalysts 35 and 36 has been developed. By
changing the protecting groups on HQ from methyl ethers to THP and opti-
mizing the Suzuki coupling the catalysts could be prepared in good overall
yields from inexpensive starting materials.
48
6. Water Oxidation Catalysts Based
on Imidazole-Containing Ligands
(Papers V, VI)
6.1 Introduction
In the search for a catalyst for water oxidation, ruthenium complex 60 has re-
cently been prepared and studied in the group. 61 A manganese complex of the
same ligand (61) has also been prepared previously. 62 Unfortunately, none of
these succeeded in catalyzing water oxidation. The failure has been attributed
to the benzylic amines present in ligand 61, which are oxididatively sensitive
and could readily be degraded under the strongly oxidative conditions required
for water oxidation.
+
O O OH HO
OO
O O
Ru Ru
N O N N OH N
N N N N
60 61
49
were then transformed into imidazole groups by refluxing in xylene together
with ammonium acetate, according to a modification of a published procedure
for similar substrates. 63 The rather moderate yield (33 %) could be attributed
to the formation of significant quantities of byproducts containing oxazole
groups instead of the desired imidazoles. Demethylation of the protected lig-
and 66 was first attempted using BBr3 in DCM, but this resulted in a com-
plex mixture from which ligand 62 was isolated in low yield (∼ 20 %) by a
tedious purification procedure involving multiple recrystallizations. In con-
trast, when 66 was refluxed in concentrated HI, the demethylation proceeded
smoothly and cleanly, and the deprotected ligand 62 was isolated in good yield
and excellent purity as the hydroiodide salt by a simple recrystallization from
methanol/acetone.
OMe MeO
O OMe O O O
1) Cs2CO3, EtOH O OMe O
HO OH
2) OMe O O O
Br
64
65 63
DMF
92 % NH4OAc
33 % xylene
reflux
OH HO OMe MeO
HI (conc)
reflux
N OH N N OMe N
N N 64 % N N
H H 1.5 HI H H
62 66
Despite being relatively short, the synthesis of ligand 62 still involves mul-
tiple steps and suffers from the low yield and difficult purification of the pro-
tected ligand 66. Based on a recently published procedure for the preparation
of benzimidazoles, 64 a similar ligand (67) was thus designed and synthesized.
Ligand 67 was prepared in a single step from dialdehyde 68 and o-nitroaniline
69, via a reductive cyclization reaction utilizing Na2 S2 O4 as the reducing
agent (Scheme 6.2). Gratifyingly, the product precipitated directly from the
reaction mixture, affording ligand 67 in good yield and purity without the
need for further purification.
50
COOH HOOC
Na2S2O4
OH COOH
EtOH, H2O
OHC CHO NH2 NH OH HN
70 °C
replacements + N N
NO2 71 %
68 69
67
L= N HO
H
N N
1) Ru(DMSO)4Cl2 L
N O N
OH HO Et3N, MeOH,
reflux Ru
O I L
N OH N O
2) 4-picoline L
reflux Ru
N N 1.5 HI
H H 3) H2O, rt N O N
L
quant. N N
62 H H
OH
70
Despite the ambiguity about the structure of complex 70, testing for wa-
ter oxidation activity was conducted, initially employing Ru(bpy)3 (PF6 )3 as
a stoichiometric one-electron oxidant in aqueous phosphate buffer (0.1 M,
pH = 7.2). This resulted in oxygen evolution with a TON of ca 100, as mea-
sured by MS. Encouraged by this result, we decided to study light-driven wa-
ter oxidation, initially using Ru(bpy)3 (PF6 )2 as photosensitizer and Na2 S2 O8
as electron acceptor. When the light was switched on, oxygen evolution could
51
be detected with a TON of ca 30. Substituting the sensitizer, however, for
the more strongly oxidizing Ru(bpy)2 (deeb)(PF6 )2 (deeb = 4,4’-bis(ethoxy-
carbonyl)-2,2’-bipyridine), increasing the redox potential from +1.26 V 36 to
+1.40 V 35 vs NHE, greatly improved the water oxidation, resulting in a TON
of ca 250 (Figure 6.2). To show that the formed oxygen originates from wa-
ter, the light-driven oxidation with Ru(bpy)2 (deeb)(PF6 )2 was repeated with
18O-labeled water (4.5 % H 18 O). The ratio 16,18O / 16,16O in the evolved oxy-
2 2 2
gen was determined to be 0.094, which corresponds to the theoretical ratio
(2 · 0.045/(1 − 0.045) = 0.094) when all oxygen is derived from water (Fig-
ure 6.3).
52
Figure 6.3: Light-driven water oxidation catalyzed by complex 70 (4.8 µ M), in an
aqueous phosphate buffer solution (0.1 M, pH = 7.2, 0.46 ml) containing 4.5 % 18O,
in the presence of Ru(bpy)2 (deeb)(PF6 )2 (110 µ M) as photosensitizer and Na2 S2 O8
(21 mM) as electron acceptor.
O L L O
Mn(OAc)2
COOH HOOC NaOAc O O O
MeOH Mn Mn
NH OH HN N O N
79 %
N N N N
H
67 L = MeOH 71
53
Figure 6.4: X-ray crystal structure of complex 71 at 50 % probability level.
H
N
N
N L O L
Mn Mn N
O O
O O O
O O O
O O
Mn Mn
N
L O L N
N
N
H
L = MeOH
observed ratio 16,18O2 / 16,16O2 was 0.10, which is close to the theoretical
ratio (2 · 0.058/(1 − 0.058) = 0.12), when all oxygen originates from
water. Light-induced water oxidation was also investigated, first using
Ru(bpy)3 (PF6 )2 , resulting in oxygen formation with a TON of ca 1. Changing
to the more strongly oxidizing Ru(bpy)2 (deeb)(PF6 )2 led to an increase of the
TON to ca 4 (Figure 6.7).
The properties of complex 71 in solution were studied by 1H NMR spec-
troscopy and X-band electron paramagnetic resonance (EPR) spectroscopy, in
D2 O and H2 O, respectively, in the presence of K3 PO4 . The relatively narrow
chemical shift range in combination with the absence of any EPR signal at
77 K indicate the presence of an antiferromagnetically coupled Mn2III,III com-
plex with a singlet ground state, i.e. the Mn2II,III complex 71 has been oxidized
in solution to Mn2III,III . The broadening of the NMR signals could be attributed
54
Figure 6.6: Oxygen evolution using Ru(bpy)33+ as stoichiometric oxidant. A solution
of complex 71 (0.5 ml, 84 µ M) in phosphate buffer (0.1 M, pH = 7.2) was injected to
Ru(bpy)3 (PF6 )3 (20 mg, 20 µ mol) at t = 0. The jump at t = 45 min is due to bursting
of gas bubbles.
to the population of excited spin states at ambient temperature. The EPR spec-
trum recorded in dimethyl sulfoxide (DMSO) at 77 K, however, shows a broad
(100 mT) signal at g = 2.0, indicative of a Mn2II,III complex. 65
The NMR spectra recorded at 25 ◦C and low concentrations of complex
71 show three broad signals with chemical shifts at 7.52, 7.31, and 6.69 ppm
(Figure 6.8). The chemical shifts were shown to be essentially independent
of the concentration of complex 71, suggesting that the ligand backbone of
complex 71 is intact in solution, under conditions similar to those used in the
water oxidation experiments, i.e. there is no rapid equilibrium between the
complex and the uncoordinated ligand. However, at higher concentrations a
set of three new, very broad signals was observed. This could be attributed
to an equilibrium between the monomeric and dimeric forms of complex 71
in solution. At low concentration the monomer should be favored, giving rise
to the initial set of three signals, while at higher concentrations a mixture of
monomer and dimer could be observed. In addition, NMR spectra recorded at
different temperatures (5, 25, 50, and 80 ◦C) indicate that the dimerization is
favored at higher temperatures, possibly due to entropy effects as coordinated
solvent molecules are released into solution.
55
Figure 6.7: Light-driven oxygen evolution catalyzed by complex 71. A solution of
complex 71 (1.0 ml, 84 µ M) in phosphate buffer (0.1 M, pH = 7.2) was injected to
Na2 S2 O8 (4.7 mg, 20 µ mol) and Ru(bpy)2 (deeb)(PF6 )2 in acetonitrile (50 µ l, 10 mM).
Light was switched on at t = 0.
6.3 Conclusions
Two new catalysts for water oxidation have been developed. The first,
ruthenium-based, catalyst was shown to catalyze highly efficient water
oxidation with a TON of ca 250, induced by visible light. The second,
manganese-based, catalyst having a tetranuclear structure reminiscent
of the Mn4 Ca cluster in the OEC is, to the best of of our knowledge,
the first homogeneous manganese complex to catalyze water oxidation
using a one-electron oxidant, and more importantly, using visible light in
combination with a photosensitizer.
56
10 9 8 7 6 5 4 3 2 1 0 −1 ppm
Figure 6.8: 1H NMR spectrum of 71 (1.0 mg) in D2 O (0.5 ml) containing K3 PO4
(1.0 mg) at 25 ◦C.
57
Acknowledgements
• Bao-Lin Lee, Docent Timofei Privalov, Dr. Torbjörn Åkermark, Dr. Junliang
Sun, Docent Örjan Hansson, Markus Kärkäs, and Eric Johnston for fruitful
collaboration.
59
References
[2] (a) Muzart, J. Chem. Rev. (Washington, DC, U. S.) 1992, 92, 113–140;
(b) Sheldon, R. A.; Kochi, J. K. Metal-catalyzed Oxidations of Organic
Compounds; Academic Press: New York, 1981.
[4] Piera, J.; Bäckvall, J.-E. Angew. Chem., Int. Ed. 2008, 47, 3506–3523.
[6] Piera, J.; Närhi, K.; Bäckvall, J.-E. Angew. Chem., Int. Ed. 2006, 45,
6914–6917.
[7] Csjernyik, G.; Éll, A. H.; Fadini, L.; Pugin, B.; Bäckvall, J.-E. J. Org.
Chem. 2002, 67, 1657–1662.
[8] Samec, J. S. M.; Éll, A. H.; Bäckvall, J.-E. Chem. Eur. J. 2005, 11, 2327–
2334.
[9] (a) Smidt, J.; Hafner, W.; Jira, R.; Sedlmeier, J.; Sieber, R.; Rüttinger, R.;
Kojer, H. Angew. Chem. 1959, 71, 176–182; (b) Bäckvall, J.-E.; Åker-
mark, B.; Ljunggren, S. O. J. Am. Chem. Soc. 1979, 101, 2411–2416; (c)
Stille, J. K.; Divakaruni, R. J. Am. Chem. Soc. 1978, 100, 1303–1304.
[10] Franzén, J.; Bäckvall, J.-E. J. Am. Chem. Soc. 2003, 125, 6056–6057.
[11] (a) Romão, C. C.; Kühn, F. E.; Herrmann, W. A. Chem. Rev. (Washing-
ton, DC, U. S.) 1997, 97, 3197–3246; (b) Beattie, I. R.; Jones, P. J. Inorg.
Chem. (Washington, DC, U. S.) 1979, 18, 2318–2319.
[12] Owens, G. S.; Arias, J.; Abu-Omar, M. M. Catal. Today 2000, 55, 317–
363.
61
[14] Herrmann, W. A.; Fischer, R. W.; Scherer, W.; Rauch, M. U. Angew.
Chem. 1993, 105, 1209–1212.
[16] Herrmann, W. A.; Fischer, R. W.; Marz, D. W. Angew. Chem., Int. Ed.
Engl. 1991, 30, 1638–1641.
[18] Rudolph, J.; Reddy, K. L.; Chiang, J. P.; Sharpless, K. B. J. Am. Chem.
Soc. 1997, 119, 6189–6190.
[19] Chow, J.; Kopp, R. J.; Portney, P. R. Science (Washington, DC, U. S.)
2003, 302, 1528–1531.
[20] (a) Balzani, V.; Credi, A.; Venturi, M. ChemSusChem 2008, 1, 26–58;
(b) Lewis, N. S.; Nocera, D. G. Proc. Natl. Acad. Sci. U. S. A. 2006, 103,
15729–15735.
[21] Ball, M.; Wietschel, M. The hydrogen economy: opportunities and chal-
lenges; Cambridge University Press, 2009.
[22] (a) Gersten, S. W.; Samuels, G. J.; Meyer, T. J. J. Am. Chem. Soc. 1982,
104, 4029–4030; (b) Gilbert, J. A.; Eggleston, D. S.; Murphy, W. R.;
Geselowitz, D. A.; Gersten, S. W.; Hodgson, D. J.; Meyer, T. J. J. Am.
Chem. Soc. 1985, 107, 3855–3864; (c) Meyer, T. J. Acc. Chem. Res.
1989, 22, 163–170.
[23] Collin, J. P.; Sauvage, J. P. Inorg. Chem. (Washington, DC, U. S.) 1986,
25, 135–141.
[24] (a) Zong, R.; Thummel, R. P. J. Am. Chem. Soc. 2005, 127, 12802–
12803; (b) Deng, Z.; Tseng, H.; Zong, R.; Wang, D.; Thummel, R. Inorg.
Chem. (Washington, DC, U. S.) 2008, 47, 1835–1848.
[25] Romero, I.; Rodríguez, M.; Sens, C.; Mola, J.; Kollipara, M. R.;
Francàs, L.; Mas-Marza, E.; Escriche, L.; Llobet, A. Inorg. Chem.
(Washington, DC, U. S.) 2008, 47, 1824–1834.
[26] Sala, X.; Romero, I.; Rodríguez, M.; Escriche, L.; Llobet, A. Angew.
Chem., Int. Ed. 2009, 48, 2842–2852.
[27] Tinker, L. L.; McDaniel, N. D.; Bernhard, S. J. Mater. Chem. 2009, 19,
3328.
62
[28] Geletii, Y. V.; Botar, B.; Kögerler, P.; Hillesheim, D. A.; Musaev, D. G.;
Hill, C. L. Angew. Chem., Int. Ed. Engl. 2008, 47, 3896–3899.
[29] Geletii, Y. V.; Huang, Z.; Hou, Y.; Musaev, D. G.; Lian, T.; Hill, C. L. J.
Am. Chem. Soc. 2009, 131, 7522–7523.
[30] Sartorel, A.; Carraro, M.; Scorrano, G.; Zorzi, R. D.; Geremia, S.; Mc-
Daniel, N. D.; Bernhard, S.; Bonchio, M. J. Am. Chem. Soc. 2008, 130,
5006–5007.
[32] Kohl, S. W.; Weiner, L.; Schwartsburd, L.; Konstantinovski, L.; Shi-
mon, L. J. W.; Ben-David, Y.; Iron, M. A.; Milstein, D. Science (Wash-
ington, DC, U. S.) 2009, 324, 74–77.
[33] Xu, Y.; Åkermark, T.; Gyollai, V.; Zou, D.; Eriksson, L.; Duan, L.;
Zhang, R.; Åkermark, B.; Sun, L. Inorg. Chem. (Washington, DC, U.
S.) 2009, 48, 2717–2719.
[34] Xu, Y.; Fischer, A.; Duan, L.; Tong, L.; Gabrielsson, E.; Åkermark, B.;
Sun, L. Angew. Chem., Int. Ed. 2010, 49, 8934–8937.
[35] Xu, Y.; Duan, L.; Tong, L.; Åkermark, B.; Sun, L. Chem. Commun.
(Cambridge, U. K.) 2010, 46, 6506–6508.
[36] Duan, L.; Xu, Y.; Zhang, P.; Wang, M.; Sun, L. Inorg. Chem. (Washing-
ton, DC, U. S.) 2010, 49, 209–215.
[38] Hull, J. F.; Balcells, D.; Blakemore, J. D.; Incarvito, C. D.; Eisen-
stein, O.; Brudvig, G. W.; Crabtree, R. H. J. Am. Chem. Soc. 2009, 131,
8730–8731.
[39] Kanan, M. W.; Nocera, D. G. Science (Washington, DC, U. S.) 2008, 321,
1072–1075.
[40] Yin, Q.; Tan, J. M.; Besson, C.; Geletii, Y. V.; Musaev, D. G.;
Kuznetsov, A. E.; Luo, Z.; Hardcastle, K. I.; Hill, C. L. Science (Wash-
ington, DC, U. S.) 2010, 328, 342–345.
[41] Ferreira, K. N.; Iverson, T. M.; Maghlaoui, K.; Barber, J.; Iwata, S. Sci-
ence (Washington, DC, U. S.) 2004, 303, 1831–1838.
63
[42] Cox, P. A. The Elements: Their Origin, Abundance, and Distribution;
Oxford University Press, USA, 1989.
[43] (a) Limburg, J.; Vrettos, J. S.; Liable-Sands, L. M.; Rheingold, A. L.;
Crabtree, R. H.; Brudvig, G. W. Science (Washington, DC, U. S.) 1999,
283, 1524–1527; (b) Limburg, J.; Vrettos, J. S.; Chen, H.; de Paula, J. C.;
Crabtree, R. H.; Brudvig, G. W. J. Am. Chem. Soc. 2001, 123, 423–430;
(c) Baffert, C.; Romain, S.; Richardot, A.; Leprêtre, J.-C.; Lefebvre, B.;
Deronzier, A.; Collomb, M.-N. J. Am. Chem. Soc. 2005, 127, 13694–
13704; (d) Tagore, R.; Chen, H.; Zhang, H.; Crabtree, R. H.; Brud-
vig, G. W. Inorg. Chim. Acta 2007, 360, 2983–2989.
[44] (a) Poulsen, A. K.; Rompel, A.; McKenzie, C. J. Angew. Chem., Int. Ed.
2005, 44, 6916–6920; (b) Baffert, C.; Collomb, M.-N.; Deronzier, A.;
Kjærgaard-Knudsen, S.; Latour, J.-M.; Lund, K. H.; McKenzie, C. J.;
Mortensen, M.; Nielsen, L. P.; Thorup, N. Dalton Trans. 2003, 1765–
1772.
[45] (a) Kurz, P.; Berggren, G.; Anderlund, M. F.; Styring, S. Dalton
Trans. 2007, 2007, 4258–4261; (b) Beckmann, K.; Uchtenhagen, H.;
Berggren, G.; Anderlund, M. F.; Thapper, A.; Messinger, J.; Styring, S.;
Kurz, P. Energy Environ. Sci. 2008, 1, 668.
[46] Gao, Y.; Åkermark, T.; Liu, J.; Sun, L.; Åkermark, B. J. Am. Chem. Soc.
2009, 131, 8726–8727.
[47] Sridharan, V.; Menéndez, J. C. Chem. Rev. (Washington, DC, U. S.) 2010,
110, 3805–3849.
[48] DeSimone, R. E.; Drago, R. S. J. Am. Chem. Soc. 1970, 92, 2343–2352.
[49] Piera, J.; Persson, A.; Caldentey, X.; Bäckvall, J.-E. J. Am. Chem. Soc.
2007, 129, 14120–14121.
[51] (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648; (b) Lee, C.; Yang, W.;
Parr, R. G. Phys. Rev. B: Condens. Matter Mater. Phys. 1988, 37, 785.
[53] (a) Hehre, W. J. J. Chem. Phys. 1972, 56, 2257; (b) Francl, M. M. J.
Chem. Phys. 1982, 77, 3654; (c) Hariharan, P. C.; Pople, J. A. Theor.
Chim. Acta 1973, 28, 213–222.
64
[54] (a) Tannor, D. J.; Marten, B.; Murphy, R.; Friesner, R. A.; Sitkoff, D.;
Nicholls, A.; Honig, B.; Ringnalda, M.; Goddard, W. A. J. Am. Chem.
Soc. 1994, 116, 11875–11882; (b) Marten, B.; Kim, K.; Cortis, C.; Fries-
ner, R. A.; Murphy, R. B.; Ringnalda, M. N.; Sitkoff, D.; Honig, B. J.
Phys. Chem. 1996, 100, 11775–11788; (c) Cramer, C. J.; Truhlar, D. G.
Chem. Rev. (Washington, DC, U. S.) 1999, 99, 2161–2200.
[55] Murray, R. W.; Iyanar, K.; Chen, J.; Wearing, J. T. Tetrahedron Lett.
1995, 36, 6415–6418.
[56] (a) Bianchini, G.; Crucianelli, M.; Angelis, F. D.; Neri, V.; Sal-
adino, R. Tetrahedron Lett. 2005, 46, 2427–2432; (b) Bianchini, G.; Cru-
cianelli, M.; Canevali, C.; Crestini, C.; Morazzoni, F.; Saladino, R. Tetra-
hedron 2006, 62, 12326–12333.
[57] Zauche, T. H.; Espenson, J. H. Inorg. Chem. (Washington, DC, U. S.)
1998, 37, 6827–6831.
[58] (a) Murray, R. W.; Jeyaraman, R.; Mohan, L. J. Am. Chem. Soc. 1986,
108, 2470–2472; (b) Mello, R.; Fiorentino, M.; Fusco, C.; Curci, R. J.
Am. Chem. Soc. 1989, 111, 6749–6757.
[59] Grennberg, H.; Faizon, S.; Bäckvall, J.-E. Angew. Chem., Int. Ed. Engl.
1993, 32, 263–264.
[60] Purse, B.; Tran, L.-H.; Piera, J.; Åkermark, B.; Bäckvall, J.-E. Chem.
Eur. J. 2008, 14, 7500–7503.
[61] Lee, B.-L.; Kärkäs, M. D.; Johnston, E. V.; Inge, A. K.; Tran, L.-H.;
Xu, Y.; Hansson, Ö.; Zou, X.; Åkermark, B. Eur. J. Inorg. Chem. 2010,
2010, 5462–5470.
[62] Anderlund, M. F.; Zheng, J.; Ghiladi, M.; Kritikos, M.; Rivière, E.;
Sun, L.; Girerd, J.-J.; Åkermark, B. Inorg. Chem. Commun. 2006, 9,
1195–1198.
[63] Poitout, L.; Roubert, P.; Contour-Galcéra, M.-O.; Moinet, C.; Lannoy, J.;
Pommier, J.; Plas, P.; Bigg, D.; Thurieau, C. J. Med. Chem. 2001, 44,
2990–3000.
[64] Yang, D.; Fokas, D.; Li, J.; Yu, L.; Baldino, C. M. Synthesis 2005, 47–56.
[65] Anderlund, M. F.; Högblom, J.; Shi, W.; Huang, P.; Eriksson, L.;
Weihe, H.; Styring, S.; Åkermark, B.; Lomoth, R.; Magnuson, A. Eur.
J. Inorg. Chem. 2006, 2006, 5033–5047.
[66] Trost, B. M.; McEachern, E. J. J. Am. Chem. Soc. 1999, 121, 8649–8650.
[67] Trost, B. M.; Ito, N.; Greenspan, P. D. Tetrahedron Lett. 1993, 34, 1421–
1424.
65