PF6 as a catalyst precursor for the one-pot direct C-H alkenylation of nitrogen heterocycles

Article abstract of DOI:10.1039/c3dt52984c

The ruthenium naphthalene complex [Ru(η⁵-C₅H ₅)(η⁶-C₁₀H₈)]⁺ is a catalyst precursor for the direct C-H alkenylation of pyridine and related nitrogen heterocycles by terminal alkynes. Stoichiometric studies have demonstrated that the naphthalene ligand may be displaced by either pyridine, 4-methylpyridine or dimethylaminopyridine (DMAP) to give species [Ru(η⁵-C₅H₅)L₃]⁺ (L = nitrogen-based ligand). Reaction of in situ-generated [Ru(η⁵- C₅H₅)(py)₃]⁺ (py = pyridine) with PPh₃ results in the formation of [Ru(η⁵-C ₅H₅)(PPh₃)(py)₂]⁺, the active catalyst for direct alkenylation, some [Ru(η⁵-C ₅H₅)(PPh₃)₂(py)]⁺ is also formed in this reaction. A one-pot procedure is reported which has allowed for the nature of the nitrogen heterocycle and phosphine ligand to be evaluated. The sterically demanding phosphine PCy₃ inhibits catalysis, and only trace amounts of product are formed when precursors containing a pentamethylcyclopentadienyl group were used. The greatest conversion was observed with PMe₃ when used as co-ligand with [Ru(η⁵- C₅H₅)(η⁶-C₁₀H₈)] ⁺.

Full text of DOI:10.1039/c3dt52984c

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ARTICLE TYPE
[Ru(η5ꢀC5H5)(η6ꢀC10H8)][PF6] as a catalyst precursor for the oneꢀpot
direct CꢀH alkenylation of nitrogen heterocycles.
Jason M. Lynam,* Lucy M. Milner, Neetisha S. Mistry, John M. Slattery,* Sally R. Warrington and
Adrian C. Whitwood.
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
The ruthenium naphthalene complex [Ru(η5ꢀC5H5)(η6ꢀC10H8)]+ is a catalyst precursor for the direct CꢀH
alkenylation of pyridine and related nitrogen heterocycles by terminal alkynes. Stoichiometric studies
have demonstrated that the naphthalene ligand may be displaced by either pyridine, 4ꢀmethylpyridine or
10 dimethylaminopyridine (DMAP) to give species [Ru(η5ꢀC5H5)L3]+ (L = nitrogenꢀbased ligand). Reaction
of in situ-generated [Ru(η5ꢀC5H5)(py)3]+ (py = pyridine) with PPh3 results in the formation of [Ru(η5ꢀ
C5H5)(PPh3)(py)2]+, the active catalyst for direct alkenylation, some [Ru(η5ꢀC5H5)(PPh3)2(py)]+ is also
formed in this reaction. A oneꢀpot procedure is reported which has allowed for the nature of the nitrogen
heterocycle and phosphine ligand to be evaluated. The sterically demanding phosphine PCy3 inhibits
15 catalysis, and only trace amounts of product are formed when precursors containing a
pentamethylcyclopentadienyl group were used. The greatest conversion was observed with PMe3 when
used as coꢀligand with [Ru(η5ꢀC5H5)(η6ꢀC10H8)]+.
Introduction
20 The direct functionalisation of carbonꢀhydrogen bonds provides
an atomꢀ and stepꢀefficient method for structural elaboration.1
However, one of the key challenges faced in the development of
such procedures is ensuring that activation of the substrate occurs
at the desired site. A popular method to circumvent this issue has
25 involved the use of directing groups which template the
coordination of the substrate to a metal catalyst and hence the site
of activation.2
We have recently reported an alternative method to achieve the
chemoselective CꢀH functionalisation of nitrogen heterocycles
30 which relies on the ability of a ruthenium halfꢀsandwich complex
to promote the conversion of pyridine to its carbeneꢀcontaining
tautomer, pyridylidene.3 Building on results initially published
45
by Murakami and Hori,4 our mechanistic study focused on
understanding the direct alkenylation of pyridine (Scheme 1)
35 which demonstrated that the active catalyst for this process was
Scheme 1
Having established the key mechanistic steps for the direct
alkenylation of pyridine, the development of a structureꢀactivity
relationship for the catalyst was desirable for further catalyst
50 optimisation. To facilitate the rapid screening of conditions and
substrates, a readily available precursor to the catalytically active
species was required. The preparation of [1aPh]+ requires the
reaction of [Ru(η5ꢀC5H5)(NCMe)3]+, [5]+, with precisely one
equivalent of PPh3 to afford [Ru(η5ꢀC5H5)(PPh3)(NCMe)2]+,
55 [6Ph]+.5 Subsequent reaction with a large excess of pyridine
results in the formation of [1aPh]+ (Scheme 2). However, a one
pot method to generate the active catalyst from a readilyꢀavailable
[Ru(η5ꢀC5H5)(PPh3)(py)2]+, [1aPh]+.
A
combination of
experimental and theoretical studies indicated that the key steps
in the activation and functionalization of the pyridine involve the
formation of the pyridylidene complex A. Complex A ultimately
40 leads to B (or its neutral pyridyl analogue) which allows
pyridylidene (or pyridyl) migration to the vinylidene to create a
new CꢀC bond. In addition, a competitive catalyst deactivation
pathway was discovered which ultimately resulted in the
formation of an additional pyridylideneꢀcontaining complex C.
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precursor would be advantageous, both in terms of catalyst
optimisation studies and for the uptake of this methodology by
the synthetic community.
solution resulted in the formation of both [1aPh]+ and [Ru(η5ꢀ
C5H5)(PPh3)2(py)]+, thus demonstrating that the active catalyst for
pyridine alkenlyation could be generated in situ from [7]+.
50 Furthermore related reactions between [7]+ and 4ꢀmethylpyridine,
2b, or N,Nꢀdimethylaminopyridine (DMAP), 2d resulted in
complete conversion to [Ru(η5ꢀC5H5)(NC5H4ꢀ4ꢀR)3]+, (R = Me
[8b]+, R = NMe2 [8d]+) after 22 hours for [8b]+, and 4 hours for
[8d]+. No reaction between [7]+ and three equivalents of 2ꢀ
55 methylpyridine was observed under these conditions.
During this study crystals of [7]PF6 suitable for study by Xꢀray
diffraction were obtained serendipitously (see Supporting
Information).
5
Scheme 2 (i) + PPh3, CH2Cl2; (ii) + 100 py, CH2Cl2.
In 2004 Kündig and coꢀworkers described the synthesis of
[Ru(η5ꢀC5H5)(η6ꢀC10H8)]+, [7]+, from the reaction of ruthenocene
Development of a Catalytic Procedure
with naphthalene in the presence of Al, AlCl3 and TiCl4.6
A
60
Our original protocol for the formation of 2ꢀstyrylpyridine,
from pyridine and an alkyne involved heating the reagents in the
presence of [1aPh]+ (20 mol% relative to the alkyne) for 48 hours
at 50 °C – this resulted in 50 % conversion to the product, based
on alkyne consumed. We elected to screen the activity for
10 revised procedure employing microwave heating was
subsequently reported.7 The naphthalene ligand in [7]+ was
shown to be thermally labile as reaction with acetonitrile readily
affords [Ru(η5ꢀC5H5)(NCMe)3]+, [5]+ (in contrast with the
reaction of [Ru(η5ꢀC5H5)(η6ꢀC6H6)]+ with MeCN, which required
15 photolysis)8. The naphthalene may also be displaced by a wide
range of aromatic substrates acting as an effective formal source
of “[Ru(η5ꢀC5H5)]+”.9 In a similar vein, it was anticipated that the
naphthalene ligand in [7]+ may be replaced by pyridine (or related
heterocycles) to give compounds [Ru(η5ꢀC5H5)L3]+, [8]+ (L =
20 nitrogen heterocycle) which on reaction with PPh3 would result in
the formation of [1]+ (Scheme 3). Performing such a procedure in
a single pot would provide facile access to the desired catalyst for
the direct alkenylation of pyridine. It should also be noted that
Hintermann has employed a oneꢀpot mixture of a pyridylꢀ
25 substituted phosphine with [7]+ to perform the catalytic antiꢀ
Markovnikov hydration of terminal alkynes.10 Complex [7]+ has
65 coupling of heterocyclic substrates with HC≡CC6H4ꢀ4ꢀCF3, 3, as
this would allow for a facile determination of conversion using
19F NMR spectroscopy. The results from this study are
summarised in Table 1. Complex [7]PF6 was heated in pyridine
for 1 hour at 50 °C in order to displace the naphthalene ligand.
70 After this time one equivalent of PPh3 was added, followed by
five equivalents of 2. The reaction was then heated at 50 °C for
48 hours. A 19F NMR spectrum recorded at this stage indicated
that ca. 29 % conversion to 2ꢀstyrylpyidine 4a had occurred A
similar reaction performed at 150 °C for 16 hours also resulted in
75 the formation of some 4a but the isolated yield was poor (9 %).
An alternative procedure was therefore developed. Napthalene
complex [7]PF6 was preꢀtreated with pyridine as described
previously, then, after addition of PPh3 and 3, the reaction
mixture was heated in a microwave reactor for 20 mins, however,
80 conversion to 4a was again poor. In addition, a 31P{1H} spectrum
illustrated that significant amounts of the catalyst deactivation
product C had been formed. The effects of different phosphine
ligands were then evaluated. Repeating the reaction in the
absence of phosphine ligand, or in the presence of PCy3 did not
85 result in the formation of any 4a. In contrast, when PMe3 was
also been used as
rearrangement.11
a catalyst precursor for the Carroll
30
Scheme 3 (i) + L; (ii) + PR3
employed,
a 25 %
conversion was observed (19F NMR
spectroscopy). Use of the 2ꢀpyridylꢀsubstituted phosphine ligand
PPh2py only resulted in the formation of trace amounts of 4a after
20 mins microwave heating, however on extending the reaction to
90 40 mins, 8 % conversion was observed.
Results and Discussion
Substitution of Naphthalene by Nitrogen Heterocycles.
To ascertain if the naphthalene ligand in [Ru(η5ꢀC5H5)(η6ꢀ
From the phosphine ligands tested, the greatest conversion was
observed for PMe3, this ligand system was then employed to
evaluate other factors in the reaction. In the first instance, the
effect of catalyst loading on the reaction was evaluated. Lowering
95 catalyst loading from 20 mol% (relative to the alkyne) to 10
mol% and 5 mol% resulted in dramatic reductions in conversion
to the product (22 % and 5 % respectively). In the case when a 10
mol% catalyst loading was used, no unreacted alkyne was
observed and the quantity of the headꢀtoꢀtail alkyne dimer, 9,
100 formed was found to be 6 %, whereas for the lowest catalyst
loading (5 mol%) significant amounts of unreacted alkyne 3 (72
%) were observed. Lowering the reaction temperature to 50 °C
resulted in considerably lower conversion, even after
conventional heating for several days.
C10H8)]+, [7]+, could be substituted by an appropriate Nꢀ
35 heterocycle, a CD2Cl2 solution of the complex was treated with 3
equivalents of pyridine, 2a. The resulting NMR spectra of the
solution demonstrated that [Ru(η5ꢀC5H5)(py)3]+, [8a]+, was
present and quantitative conversion was observed after 48 hours
at room temperature. No evidence for intermediate species
40 containing both pyridine and naphthalene coordinated to the
metal was obtained. The identity of [8a]+ was supported by the
1H NMR spectrum which displayed a resonance at δΗ 4.15 for the
coordinated cyclopentadienyl ligand with peaks at δΗ 8.48, 7.83
and 7.34 for the three coordinated pyridine ligands (1H NMR
45 data12 for [Ru(η5ꢀC5H5)(py)3]+, [8a]+ in (CD3)2CO δΗ 8.72, 7.96,
7.46 and 4.24). Addition of one equivalent of PPh3 to this
,
2
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Increasing the number of equivalents of pyridine used in the 55 was explored.
reaction from 20 to 200 (equivalent to lowering the concentration
of the catalyst and alkyne) and using PMe3 as the phosphine
resulted in the greatest conversion to 4a. Under these conditions,
57% conversion was observed after 20 mins microwave heating,
and after 40 mins 79 % conversion was obtained. The reaction
was repeated with lower catalyst loadings, and heating for 1 hour,
but this resulted in a lower conversion (28 %) than in equivalent
reactions where the catalyst and alkyne concentration was higher.
(i)
(a)
Ru
Ru
Me3P
MeCN
Me3P
N
NCMe
5
N
6Me +
1aMe +
[
]
[
]
(i)
(b)
Ru
Ru
Ru
10 When PPh2py was employed under these conditions and the
reaction mixture was heated for 40 min, 42 % conversion to 4a
was observed.
iPr3P
MeCN
iPr3P
MeCN
N
N
N
NCMe
N
The alkenylation of substituted pyridine derivatives was
subsquently investigated. Using the combination of [7]PF6 and
15 PMe3 as the catalyst system and microwave irradiation for 20
minutes, reaction of 20 equivalents of either 4ꢀ or 3ꢀpicoline with
2 and heating for 40 minutes resulted in the formation of a single
product in both cases. Compounds 4b and 4c were formed – in
both cases activation at the 2ꢀposition occurs selectively and, in
20 the case of 4c only one of the two possible isomers was obtained
(Scheme 4), as was observed in Murakami and Hori’s original
procedure.4
[6iPr +
]
[10iPr +
]
[8a]+
(observed after addition of further py)
Me
Me
Me
Me
Me
Me
iPr3P
Me
Me
Me
(i)
(c)
Me
Ru
Ru
iPr3P
MeCN
N
NCMe
MeCN
6Ph* +
10Ph* +
]
[
]
[
Scheme 4. (i) + 100 py, CH2Cl2.
In a similar vein to the chemistry previously reported with
PPh3, the reaction of [Ru(η5ꢀC5H5)(PMe3)(NCMe)2]PF6, [6Me]PF6
60 with an excess of pyridine resulted in the formation [Ru(η5ꢀ
C5H5)(PMe3)(py)2]+, [1aMe]PF6, (Scheme 4a) which could be
isolated in good yield. The complexes were identified by NMR
spectroscopy where characteristic resonances for coordinated
pyridine were observed at δH 7.28, 7.81 and 8.41. The structure of
65 [1aMe]PF6 was confirmed by single crystal Xꢀray analysis and the
molecular structure of the [1aMe] cation is shown in Figure 1.
CF3
(i)
N
N
+
CF3
Me
Me
4c
2c
Scheme 4 (i) [7]PF6 (20 mol%), PMe3 (20 mol %), microwave
25
heating, 20 mins, 150 °C
Pentamethylcyclopentadienyl Complexes
The effect of substituting the cyclopentadienyl ring with its
pentamethylcyclopentadienyl analogue was investigated. In this
case, [Ru(η5ꢀC5Me5)(NCMe)3]+ , [5*]+, was used as catalyst
30 precursor. The reaction was performed in pyridine solution (200
equivalents) with PPh3 as the phosphine and microwave heating
for 20 mins. Although some 4a was formed, as shown by ESIꢀMS
and TLC analysis, the reaction was unselective and a number of
other fluorineꢀcontaining products were obtained. In a similar
35 vein, using conventional heating at 50 °C for 16 hours with any
of [Ru(η5ꢀC5Me5)(PPh3)(NCMe)2]PF6, [6Ph*]PF6, [Ru(η5ꢀ
C5Me5)(PMe3)(NCMe)2]PF6,
[6Me*]PF6
or
[Ru(η5ꢀ
C5Me5)(PPh3)(NCMe)(py)]PF6 [10Ph*]PF6 as catalyst (20 mol%)
in pyridine solution only resulted in trace amounts of 4a being
40 formed as shown by ESIꢀMS and TLC analysis. Even after
heating the reactions in which [6Ph*]PF6 or [6Me*]PF6 were
employed, for 72 hours at 50 °C the 19F NMR spectrum still
exhibited a significant peak for unreacted alkyne 2. We therefore
concluded
that
complexes
containing
the
Figure 1. Solidꢀstate structure of the cation [1aMe]+. Hydrogen atoms and
anion have been omitted for clarity, and the thermal ellipsoids are at the
45 pentamethylcyclopentadienyl ligand were poor catalysts for this
reaction, both in terms of the rate of alkenylation and the
formation of side products.
70
50 % probability level.
PyridineꢀSubstitution Studies
In contrast, an identical reaction between [Ru(η5ꢀ
C5H5)(PiPr3)(NCMe)2]PF6, [6iPr]PF6 and pyridine did not result in
a selective reaction (Scheme 4b). An examination of the crude
The
poor
catalyst
activity
observed
for
the
50 pentamethylcyclopentadienyl derivatives or when PCy3 is used,
appears to indicate that steric effects may be important in
dictating catalyst behaviour. In order to investigate if this was
indeed the case, the substitution of the acetonitrile ligands by
1
reaction by H and 31P NMR spectroscopy indicated that several
75 products were present, in addition to unreacted starting material.
The dominant set of resonances were consistent with the
pyridine in the complexes [Ru(η5ꢀC5R5)(PR1 )(NCMe)2]+, [6]+,
3
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formation of [Ru(η5ꢀC5H5)(PiPr3)(NCMe)(py)]+, [10iPr]PF6, as
5
evidenced by resonances at δΗ 2.54 (d, JHP = 1.2 Hz, 3H) and
4.51 (s, 5H) for acetonitrile and cyclopentadienyl ligands
respectively. Peaks for the coordinated pyridine ligand were
observed at δΗ 7.29 (2H) 7.75 (1H) and 8.71 (2H). In an attempt
to prepare [Ru(η5ꢀC5H5)(PiPr3)(py)2]+ the reaction was repeated
and the product precipitated by addition of pentane. This residue
was dissolved in CH2Cl2 and a further 50 equivalents of pyridine
added. This resulted in a reduction in intensity of the resonance
5
10 assigned to [10iPr]+, and an increase peaks at series of peaks
which were assigned to [Ru(η5ꢀC5H5)(py)3]+, [8a]+. Crystals of
[10iPr]PF6 suitable for study by Xꢀray crystallography were
obtained from a reaction between the acetonitrile complex
[6iPr]PF6 and 10 equivalents of pyridine and the cation [10iPr]+ is
15 shown in Figure 2. The structure also exhibited an area of
electron density which was modelled as [MePiPr3]PF6.
30
Figure 3. Solidꢀstate structure of one of the crystallographicallyꢀ
independent cations in the structure of [10Ph*]PF6; thermal ellipsoids
(where shown) at the 50 % probability level; hydrogen atoms and
counterꢀion omitted for clarity. Selected bond lengths (Å) N(1)ꢀRu(1)
35 2.122(6), N(2)ꢀRu(1) 2.081(7), P(1)ꢀRu(1) 2.3426(19). Selected bond
angles (°) N(1)ꢀRu(1)ꢀP(1) 90.96(16), N(2)ꢀRu(1)ꢀP(1) 83.53(18), N(1)ꢀ
Ru(1)ꢀN(2) 91.7(2).
Conclusions
We have demonstrated that it is possible to perform the catalytic
40 CꢀH functionalisation of pyridineꢀbased heterocycles using
[7]PF6 as ruthenium precursor. The results from the structural
studies demonstrate that as the steric bulk around the ruthenium is
increased it becomes progressively harder to incorporate two
pyridine ligands into the coordination sphere of the metal.
45 Combined with the results from the catalytic studies, it therefore
appears that the efficiency of the system may be linked to the
steric demands of the complex precursor and substrate; a similar
argument has been made in the case of ruthenium halfꢀsandwich
compounds which catalyse the reduction of Nꢀheterocycles by
50 silanes.14 Although one could also rationalise the behaviour in
terms of electronic effects as both the electron rich
pentamethylcyclopentadienyl and PCy3ꢀbased systems are
inactive, the high activity of the PMe3 system does not appear to
fit this electronic trend. The most effective catalyst system is
55 based on the η5ꢀC5H5/PMe3 system which we will seek to further
exploit for direct alkenylation reactions.
Figure 2. Solidꢀstate structure of the cation [10iPr]+. Hydrogen atoms and a
[PF6]ꢀ anion have been omitted for clarity, thermal ellipsoids are at the 50
20
% probability level. Additionally, a [MePiPr3]PF6 species has been
omitted.
The reaction between [Ru(η5ꢀC5Me5)(PPh3)(NCMe)2]PF6,
[6Ph*]PF6 and an excess of pyridine also did not result in the
substitution of both acetonitrile ligands. In this case, [Ru(η5ꢀ
25 C5Me5)(PPh3)(NCMe)(py)]PF6, [10Ph*]PF6, was the major product
although some unidentified organometallic complexes where also
present. This contrast markedly with the cyclopentadienyl
analogue [6Ph]PF6 which, under identical conditions, affords
[Ru(η5ꢀC5H5)(PPh3)(py)2]PF6, [1aPh*]PF6, in good yield.13
Experimental
All air sensitive experimental procedures were performed under
an inert atmosphere of dinitrogen, using standard Schlenk line
60 and glovebox techniques. Solvents were AR grade and used
without purification, or degassed by purging with dinitrogen
where stated. CDCl3 and CD2Cl2 for NMR spectroscopy was
purchased from Aldrich Chemicals. The CDCl3 was used without
further purification and the CD2Cl2 was dried over CaH2 and
65 vacuum transferred prior to use. Pyridine and 4ꢀethynylꢀα,α,αꢀ
trifluorotoluene were purchased from Acros Organics; the extra
dry pyridine was stored under
a nitrogen atmosphere.
RuCl3.3H2O was supplied from Precious Metals Online. NMR
spectra were acquired on the following: Bruker AVANCE 500
4
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(Operating frequencies 1H 500.23 MHz, 31P 202.50 MHz, 13C
Reaction of [7]PF6 with 2ꢀmethylpyridine.
125.77 MHz) or Jeol ECXꢀ400 (Operating frequencies 1H 399.78 60 To a solution of [7]PF6 (20 mg, 0.046 mmol) CD2Cl2 (0.5 ml)
MHz, 31P 161.83 MHz, 19F 376.17 MHz, 13C 100.53 MHz). 31P
and 13C spectra were recorded with proton decoupling.
Accurate mass, ESIꢀMS results were recorded on a Bruker
micrOTOF mass spectrometer, coupled to an Agilent 1200 series
LC system. EIꢀMS was recorded on a Waters GCT Premier mass
spectrometer, coupled to an Agilent 7890 GC system to provide
GCꢀEIꢀMS. Elemental analyses were performed using an Exeter
10 Analytical Inc. CEꢀ440 analyser. Column chromatography was
carried out using Fluka Silica Gel. Thin layer chromatography
used Analtech Uniplate silica gel GF prepared TLC plates (20 x
20 cm, 1000 microns thickness). Microwave reactions were
heated in a CEM Discover Microwave.
was added 2ꢀmethylpyridine (13.5 ꢁl, 0.14 mmol) in a Young’s
NMR tube. No substitution of the naphthalene ligand was
observed.
5
Typical Catalytic Procedure.
65 Under a N2 atmosphere, a microwave vial was charged with
[7]PF6 (0.0527 g, 0.12 mmol) and pyridine (970 ꢀl, 120 mmol)
and heated at 50 °C for 1 hour. Trimethylphosphine (12.4 ꢂl, 0.12
mmol) was added to the reaction mixture, followed by 4ꢀethynylꢀ
α,α,αꢀtrifluorotoluene, 2, (97.8 ꢂl, 0.6 mmol) before microwave
70 irradiation at 150 °C for 20 minutes. The product, 4a, was then
isolated by one of the following methods: Preparative TLC – The
crude reaction mixture was dried in vacuo, and then redissolved
in dichloromethane (10 ml). The crude reaction mixture was
applied to a silica column, and eluted using a solvent mixture of
75 3:1 pentane to ethyl acetate. Isolated yield = 31 mg, 21 %. The
percentage conversion was calculated by19F NMR (79 %).
15
Single crystal Xꢀray diffraction was carried out on an Oxford
Diffraction SuperNova diffractometer with molybdenum
a
source. The crystals were kept at 110.00(10) K during data
collection. The crystal was cooled with an Oxford Instruments
Cryojet. Diffractometer control, data collection, initial unit cell
Synthesis of [Ru(η5ꢀC5H5)(PMe3)(py)2]PF6, [1aMe]PF6 To a
solution of [Ru(η5ꢀC5H5)(PMe3)(NCMe)2][PF6] (108 mg, 0.23
mmol) in dichloromethane (5 ml), pyridine (1.8 ml, 22 mmol, 97
80 equiv) was added and the reaction mixture stirred (3 hours). Slow
diffusion of pentane in to the reaction mixture afforded orange
crystals, suitable for Xꢀray crystallography. The solvent was
removed by filtration and the airꢀsensitive product dried under
20 determination, frame integration and unitꢀcell refinement was
carried out with “Crysalis”.15
Faceꢀindexed absorption
corrections were applied using spherical harmonics, implemented
in SCALE3 ABSPACK scaling algorithm.16 Using Olex2,17 the
structures were solved with either the Superflip structure solution
25 program using Charge Flipping or the XS structure solution
program using Direct Methods or the Patterson Method. They
were refined with the ShelXL refinement package using Least
Squares minimisation.3 Details of the data collection and
structure refinement are presented in Table 2. CCDC 967802
1
vacuum. Yield (83 mg, 66 %). H NMR (CD2Cl2, 500 MHz, 295
85 K): δ 1.40 (d, 9H, 2JHP = 26.3 Hz, PMe3), 4.39 (s, 5H, C5H5), 7.28
3
4
(m, 4H, pyꢀH3), 7.81 (tt, 2H, JHH = 7.6 Hz, JHH = 1.5 Hz, pyꢀ
H4), 8.41 (m, 4H, pyꢀH2). 31P{1H} NMR (CD2Cl2, 202 MHz, 295
30 ([1aMe]PF6),
967803
[10iPr]PF6.[MePiPr3]PF6,
967804
1
ꢀ
K): ꢀ144.4 (sept, JPF = 710 Hz, PF6 ), 3.1 (s, PMe3). 13C{1H}
([10Ph*]PF6) and 967805 ([7]PF6) contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
1
NMR (125 MHz, 295 K, CD2Cl2): 17.9 (d, JCP = 26.3 Hz,
2
90 PMe3), 76.0 (d, JCP = 2.3 Hz, C5H5), 126.0 (s, pyꢀC3), 137.4 (s,
3
pyꢀC4), 156.7 (d, JCP = 2.8 Hz, pyꢀC2). ESI MS (m/z): Observed
401.0717 [M+], Expected C18H24N2P102Ru 401.0720, Error = 0.3
mDa; Observed 363.0568 [M+ ꢀNC5H5 +NCMe], Expected
C15H22N2P102Ru 363.0559, Error = 0.9 mDa; Observed 322.0336,
95 Expected C13H19NP102Ru 322.0293, Error = 4.3 mDa. ATR IR (ν
/cmꢀ1): 700.1 (s), 757.9 (s), 824.4 (s), 837.9 (s), 879.4 (w), 953.7
(w), 1025.0 (w), 1060.7 (w), 1100.2 (w), 1214.0 (w), 1261.2 (w),
1285.3 (w), 1351.9 (w), 1427.1 (w), 1445.4 (w), 1483.0 (w),
2359.5 (w), 2966.0 (w). Elemental Analysis: Anal.
100 C18H24F6N2P2Ru: Calc. C 39.64, H 4.44, N 5.14, Found C 39.53,
H 4.32, N 5.02.
5
7
35
Complexes [6Ph]PF6 and [7]PF6 were prepared as described
previously. Complex [6Ph*]PF6 was prepared by the same
procedures used for the cyclopentadienyl analogue.5
Reaction of [7]PF6 with pyridine.
To a solution of [7]PF6 (20 mg, 0.046 mmol) in CD2Cl2 (0.4 ml)
40 was added pyridine (11.0 ꢁl, 0.14 mmol) in a Young’s NMR
tube. Quantitative conversion to [8a]+ was observed after 48
hours. 1H NMR (CD2Cl2, 400 MHz, 295 K): δ 4.15 (s, 5H, C5H5),
7.34 (m, 6H, H3), 7.68 (tt, 3JHH = 7.6 Hz, 4JHH = 1.8 Hz, 3H, H4),
8.47 (m, 6H, H2)
Spectroscopic Data for 4a
45 Reaction of [7]PF6 with 4ꢀmethylpyridine.
To a solution of [7]PF6 (20 mg, 0.046 mmol) in CD2Cl2
dichloromethane (0.4 ml) was added 4ꢀmethylpyridine(13.3 ꢁl,
0.14 mmol) in a Young’s NMR tube. Quantitative conversion to
1
[8b]+ was observed after 22 hours. H NMR (CD2Cl2, 400 MHz,
50 295 K): δ 2.39 (s, 9H, CH3), 4.07 (s, 5H, C5H5), 7.13 (m, 6H,
H3), 8.27 (m, 6H, H2).
Reaction of [7]PF6 with DMAP.
1H NMR (CDCl3, 400 MHz, 295 K): δ 7.19 (m, 1H, H2), 7.24 (d,
To a solution of [7]PF6 (20 mg, 0.046 mmol) in CD2Cl2 (0.4 ml)
was added N,Nꢀdimethylaminopyridine (DMAP) (17 mg, 0.14
55 mmol) in a Young’s NMR tube. Quantitative conversion to the
[8d]+ species was observed after 4 hours.1H NMR (CD2Cl2, 400
MHz, 295 K): δ 3.01 (s, 18H, CH3), 3.90 (s, 5H, C5H5), 6.41 (m,
6H, H3), 7.93 (m, 6H, H2).
3
3
105 JHH = 16.3 Hz, 1H, H6/7), 7.40 (d, JHH = 7.8 Hz, 1H, H4), 7.73ꢀ
3
7.59 (m, 6H, H3, H6/7, H9, H10), 8.63 (d, JHH = 4.7 Hz, 1H, H1).
13C NMR (CDCl3, 100 MHz, 295 K): δ 122.8 (s, C4), 122.8 (s,
C2), 124.3 (q, 1JCF = 272.2 Hz, C12), 125.8 (q, 4JCF = 3.9 Hz, C9),
127.3 (s, C6/7/10), 130.1 (q, 2JCF = 32.6, C11), 130.3 (s, C6/7), 131.3
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5
(s, C6/7/10), 136.9 (s, C3), 140.2 (q, JCF = 1.6 Hz, C8), 149.9 (s,
406.1232, Error = 0.4 mDa; Observed 368.1053 [M+ ꢀ NC5H5],
Expected C16H29NP102Ru 406.1232, Error = 2.3 mDa; Observed
325.0284 [Ru(η5ꢀC5H5)(NC5H5)2]+, Expected C15H15N2102Ru
325.0273, Error = 1.2 mDa
C1), 155.0 (s, C5). 19F NMR (CDCl3, 376 MHz, 295 K): δ ꢀ62.4
(s, CF3). MS (ESI+): Measured m/z = 250.0835, [M+H]+
Calculated m/z for C14H11F3N = 250.0838 (ꢁ = 0.3 mDa)
Spectroscopic Data for 4b
5
50 Synthesis of [Ru(η5ꢀC5Me5)(PPh3)(NCMe)(py)]PF6, [10Ph*]PF6
An ovenꢀdried Schlenk tube equipped with a magnetic stirring
bar was charged with [Cp*Ru(NCMe)2(PPh3)][PF6] (144 mg, 0.2
mmol), dichloromethane (5 mL), and an excess of pyridine (1.6
mL, 0.2 mmol) under an N2 atmosphere. The clear yellow
55 reaction mixture was stirred for 3 hours, after which time the
solution was concentrated and the yellow product precipitated
with pentane. The solvent was removed by cannula filtration,
before the yellow product was dried under vacuum. Yield 131
mg, 83 %. Crystals suitable for Xꢀray diffraction were grown by
60 slow diffusion of pentane into a dichloromethane solution of the
1H NMR (CDCl3, 400 MHz, 295 K): δ 2.37 (s, H4), 7.02 (d, JHH
4.6 Hz, H2), 7.37ꢀ7.16 (m, 2H, H5, H7/8), 7.68ꢀ7.57 (m, 5H, H7/8
H10, H11), 8.47 (d, JHH = 3.7 Hz, 1H, H1), 13C NMR (CDCl3, 100
=
,
complex. 1H NMR (CD2Cl2, 400 MHz, 295 K), δH 1.30 (d, 4JPH
=
5
10 MHz, 295 K): δ 21.3 (s, C4), 123.8 (s, C5), 123.9 (s, C2), 124.3 (q,
1.6 Hz, 15H, C5Me5), 2.09 (d, JPH = 1.6 Hz, 3H, NCMe), 7.00ꢀ
7.13 (m, 8H, PPh3), 7.24 – 7.36 (m, 8H, PPh3), 7.36 – 7.47 (m,
4H, PPh3), 7.57 (tt, J = 7.6 Hz, J = 1.5 Hz, 1H, pyꢀH4), 8.29 (d,
1JCF = 272.0 Hz, C13), 125.6 (q, JCF = 3.8 Hz, C10), 127.4 (s,
4
2
C7/8/11), 130.1 (q, JCF = 32.5 Hz, C12), 130.3 (s, C7/8/11), 131.3 (s,
5
3
65 JHH = 5.0 Hz, 2H, pyꢀH2). 31P{1H} NMR (CD2Cl2, 162 MHz,
C7/8/11), 140.4 (q, JCF = 1.6 Hz, C9), 148.3 (s, C3), 149.4 (s, C1),
154.7 (s, C6). 19F NMR (CDCl3, 376 MHz, 295 K): δ ꢀ62.5 (s,
15 CF3) MS (ESI+): Measured m/z = 264.0997, [M+H]+ Calculated
m/z for C15H13F3N = 264.0995 (ꢁ = 0.2 mDa)
1
ꢀ
295 K), δ: ꢀ143.5 (sept, JPF = 711 Hz, PF6 ), 51.1 (s, PPh3).
13C{1H} NMR (CD2Cl2, 162 MHz, 295 K), δ: 4.0 (s, NCMe), 9.1
2
(s, C5Me5), 86.5 (d, JCP = 2.4 Hz, C5Me5), 125.8 (s, pyꢀC4),
3
4
Spectroscopic Data for 4c
128.6 (d, JCP = 9.8 Hz, PPh3ꢀC3), 130.3 (d, JCP = 1.6 Hz, PPh3ꢀ
1
70 C4), 133.4 (s, pyꢀC3), 133.7 (s, (d, JCP = 48.1 Hz, PPh3ꢀC1),
13
11
2
133.8 (d, JCP = 10.6 Hz, PPh3ꢀC2), 155.4 (s, pyꢀC2). Elemental
CF3
10
9
12
7
Analysis: Anal. C35H38F6N2P2Ru: Calc. C 55.05, H 5.02, N 3.67,
Found C 55.75, H 5.17, N 3.70.
6
N
4
1
8
2
5
Acknowledgements
4c
3
75 We are grateful to the EPSRC (Grant EP/H011455/1, studentship
to NSM, and DTA studentship to LMM) and the University of
York for funding. We thank Mr Christopher Johnson for
experimental assistance and Professor Ian Fairlamb for access to
the microwave reactor.
1H NMR (CDCl3, 400 MHz, 295 K): δ 2.35 (s, 3H, H3), 7.22 (d,
3
3
20 JHH = 16.3 Hz, 1H, H7/8), 7.31 (d, JHH = 7.9 Hz, 1H, H4), 7.50
(d, 3JHH = 7.9 Hz, 1H, H5), 7.67ꢀ7.56 (m, 5H, H7/8, H10, H11), 8.45
(s, 1H, H1). 13C NMR (CDCl3, 100 MHz, 295 K): δ 18.5 (s, C3)
122.2 (s, C4), 124.3 (q, 1JCF = 271.9 Hz, C13), 125.8 (q, 4JCF = 3.8
2
Hz, C10), 127.3 (s, C7/8/11), 129.5 (q, JCF = 32.3 Hz, C12), 130.2
80 Notes and references
25 (s, C7/8/11), 130.3 (s, C7/8/11), 132.6 (s, C2), 137.3 (s, C5), 140.4 (q,
5JCF = 1.6 Hz, C9), 150.4 (s, C1), 152.4 (s, C6). 19F NMR (CDCl3,
376 MHz, 295 K): δ ꢀ62.4 (s, CF3) MS (ESI+): Measured m/z =
264.0994, [M+H]+ Calculated m/z for C15H13F3N = 264.0995 (ꢁ
= 0.1 mDa)
a Department of Chemistry, University of York, Heslington, York, YO10
5DD Fax: +44(0)1904322516; Tel: +44(0)1904322534; E-mail:
jason.lynam@york.ac.uk, john.slattery@york.ac.uk
† Electronic Supplementary Information (ESI) available: Details of the
85 solid state strucutre of [7]PF6, crystallographic data in CIF format. See
DOI: 10.1039/b000000x/
30 Synthesis of [Ru(η5ꢀC5H5)(PiPr3)(NCMe)(py)]PF6, [10iPr]PF6
[Ru(η5ꢀC5H5)(PiPr3)(NCMe)2][PF6] (120 mg, 0.22 mmol) was
placed in dichloromethane (5 ml). Pyridine (0.91 ml, 11.5 mmol,
50 equiv) was added to give an orange reaction mixture which
was stirred (16 hours). The solvent was removed under vacuum.
35 The reaction gave a mixture of products. The slow diffusion of
pentane into a dichloromethane layer containing a mixture of
ruthenium complexes afforded crystals of 15 suitable for Xꢀray
diffraction. 1H NMR (CD2Cl2, 500 MHz, 295 K): δ 1.09ꢀ1.17 (m,
1.(a) D. Balcells, E. Clot and O. Eisenstein, Chem. Rev., 2010, 110, 749ꢀ
823; (b) D. A. Colby, R. G. Bergman and J. A. Ellman, Chem. Rev., 2010,
90 110, 624ꢀ655; (c) R. H. Crabtree, Chem. Rev., 2010, 110, 575ꢀ575; (d) A.
Gunay and K. H. Theopold, Chem. Rev., 2010, 110, 1060ꢀ1081; (e) T. W.
Lyons and M. S. Sanford, Chem. Rev., 2010, 110, 1147ꢀ1169; (f) L.
Ackermann, Chem. Rev., 2011, 111, 1315ꢀ1345; (g) T. C. Boorman and I.
Larrosa, Chem. Soc. Rev., 2011, 40, 1910ꢀ1925; (h) J. WencelꢀDelord, T.
95 Droege, F. Liu and F. Glorius, Chem. Soc. Rev., 2011, 40, 4740ꢀ4761.
2.(a) F. Kakiuchi and S. Murai, Acc. Chem. Res., 2002, 35, 826ꢀ834; (b)
J. Dupont, C. S. Consorti and J. Spencer, Chem. Rev., 2005, 105, 2527ꢀ
2572; (c) M. J. Tredwell, M. Gulias, N. Gaunt Bremeyer, C. C. C.
Johansson, B. S. L. Collins and M. J. Gaunt, Angew. Chem., Int. Ed.,
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Chem., 2006, 4, 4041ꢀ4047; (e) O. Daugulis, H.ꢀQ. Do and D. Shabashov,
Acc. Chem. Res., 2009, 42, 1074ꢀ1086; (f) I. V. Seregin and V.
Gevorgyan, Chem. Soc. Rev., 2007, 36, 1173ꢀ1193.
3
18H, P(CHMe2)3), 2.24 (sept, 3H, JHH = 7.3 Hz, P(CHMe2)3),
40 2.54 (d, 5JHP = 1.2 Hz, NCMe), 4.51 (s, 5H, C5H5), 7.27ꢀ7.30 (m,
2H, pyꢀH4), 7.75 (tt, 1H, pyꢀH3), 8.70ꢀ8.72 (m, 2H, pyꢀH2).
1
31P{1H} NMR (CD2Cl2, 202 MHz, 295 K): ꢀ143.0 (sept, JPF
=
711 Hz, PF6 ), 52.8 (s, PiPr3). ESI MS (m/z): Observed 447.1492
[M+], Expected C21H34N2P102Ru 447.1503, Error = 1.1 mDa;
45 Observed 406.1228 [M+ ꢀ NCMe], Expected C19H31NP102Ru
ꢀ
3.D. G. Johnson, J. M. Lynam, N. S. Mistry, J. M. Slattery, R. J. Thatcher
105 and A. C. Whitwood, J. Am. Chem. Soc., 2013, 135, 2222ꢀ2234.
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DOI: 10.1039/C3DT52984C
4.M. Murakami and S. Hori, J. Am. Chem. Soc., 2003, 125, 4720ꢀ4721.
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Mereiter, R. Schmid and K. Kirchner, Organometallics, 1999, 18, 3843ꢀ
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6.E. P. Kundig and F. R. Monnier, Adv. Synth. Catal., 2004, 346, 901ꢀ
904.
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E. P. Kündig, Chem. Commun., 2009, 5227ꢀ5229.
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10 9.(a) D. S. Perekalin, E. E. Karslyan, P. V. Petrovskii, Y. V. Nelyubina,
K. A. Lyssenko, A. S. Kononikhin, E. N. Nikolaev and A. R. Kudinov,
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A. O. Borissova and A. R. Kudinov, Mendeleev Commun., 2011, 21, 82ꢀ
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Englert, Organometallics, 2009, 28, 5739ꢀ5748.
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2010, 352, 3339ꢀ3347; (b) D. Linder, F. Buron, S. Constant and J. Lacour,
25 European Journal of Organic Chemistry, 2008, 5778ꢀ5785.
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10, 770ꢀ777.
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O. V. Dolomanov, A. J. Blake, N. R. Champness and M.
35
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ARTICLE TYPE
Entry
Catalyst
(loading / mol %)
[7]PF6 (20)
[7]PF6 (20)
[7]PF6 (20)
[7]PF6 (20)
[7]PF6 (20)
[7]PF6 (20)
[7]PF6 (10)
[7]PF6 (5)
[7]PF6 (20)
[7]PF6 (20)
[7]PF6 (20)
[7]PF6 (10)
[7]PF6 (5)
[7]PF6 (20)
[7]PF6 (20)
[7]PF6 (20)
[7]PF6 (20)
[7]PF6 (20)
[7]PF6 (20)
[7]PF6 (20)
[5*]PF6 (20)
[6Ph*]PF6 (20)
[6Me*]PF6 (20)
[10Ph*]PF6 (20)
[1aMe*]PF6 (20)
Phosphine Heterocycle Temperature / °C
Time
Product
Conversion to 4 / %
(Isolated yield)
29
Unreacted 2 / %
9 / %
(Equivalents)
2a (20)
2a (20)
2a (20)
2a (20)
2a (20)
2a (20)
2a (20)
2a (20)
2a (20)
2a (200)
2a (200)
2a (200)
2a (200)
2a (200)
2a (200)
2a (200)
2b (20)
2b (20)
2c (20)
1
2
3
4
5
6
PPh3
PPh3
50
2 days
16 hrs
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4b
4b
4c
4c
4a
4a
4a
4a
4a
43
ND
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
50
Trace (9)
0
Trace
8(13)
27(21)
22
PCy3
PPh2py
PPh2py
PMe3
PMe3
PMe3
None
PMe3
PMe3
PMe3
PMe3
PMe3
PPh3
PPh2py
PMe3
PMe3
PMe3
PMe3
PPh3
20 min
20 min
40 min
20 min
20 min
20 min
20 min
20 min
40 min
60 min
60 min
40 min
40 min
40 min
20 min
40 min
40 min
40 min
20 min
16 hrs
ND
ND
ND
72
3
4
6
7
8 a
9
5
0
10
11
12
13
14b
15
16
17
18
19
20
21
22
23
24
25
57(25)
68(21)
28
22
ND
8
7
14
26
7
ꢀ(11)
Trace (2)
42
4
17
ꢀ(30)
27(22)
22(17)
ꢀ(22)
Trace
Trace
Trace
Trace
Trace
ND
ND
5
6
2c (200)
2a (200)
2a (20)
2a (20)
2a (20)
2a (20)
N/A
N/A
50
16 hrs
16 hrs
16 hrs
N/A
50
N/A
50
a
with added lutidene (20 mol%) b performed without a nitrogen atmosphere, ND not detected. All reactions performed at 150 °C (with the exception of
entry 2) utilised microwave heating.
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[1aMe]PF6
C18H24N2F6P2Ru
545.40
[10iPr]PF6.[MePiPr3]PF6
C136H228F42N12P14Ru6
3869.36
[10Ph*]PF6
C35H38F6N2P2Ru
763.68
Empirical formula
Formula weight
Temperature/K
Crystal system
Space group
110.00(10)
monoclinic
C2/c
163.0
trigonal
Rꢀ3:r
109.95(10)
triclinic
Pꢀ1
a/Å
b/Å
c/Å
α/°
31.046(3)
8.5236(7)
17.2938(12)
90.00
108.356(8)
90.00
4343.5(6)
8
1.668
16.9556(10)
16.9556(10)
16.9556(10)
105.795
105.795
105.795
4185.9(4)
1
1.5349
10.1826(2)
15.1616(4)
22.6072(12)
89.425(3)
88.941(3)
85.4958(18)
3478.7(2)
4
β/°
γ/°
Volume/Å3
Z
ρcalcmg/mm3
m/mmꢀ1
1.458
0.602
0.926
0.757
F(000)
2192.0
1975.1
1560.0
Crystal size/mm3
2Θ range for data collection
0.2498 × 0.2377 × 0.1032
6.16 to 64.52°
0.31 × 0.07 × 0.05
3.02 to 56.58°
0.1528 × 0.0964 × 0.0749
5.84 to 52.04°
ꢀ43 ≤ h ≤ 45
ꢀ9 ≤ k ≤ 12
ꢀ25 ≤ l ≤ 25
ꢀ22 ≤ h ≤ 22
ꢀ22 ≤ k ≤ 22
ꢀ22 ≤ l ≤ 21
ꢀ12 ≤ h ≤ 12
ꢀ18 ≤ k ≤ 18
ꢀ27 ≤ l ≤ 27
Index ranges
Reflections collected
Independent reflections
Data/restraints/parameters
Goodnessꢀofꢀfit on F2
22590
7006[R(int) = 0.0263]
7006/0/267
43426
6932[R(int) = 0.0808]
6932/3/319
25827
13625[R(int) = 0.0441]
13625/30/854
1.170
1.037
1.041
R1 = 0.0239
wR2 = 0.0529
R1 = 0.0461
wR2 = 0.1010
R1 = 0.0881
wR2 = 0.1787
Final R indexes [I>=2σ (I)]
R1 = 0.0280
wR2 = 0.0553
0.50/ꢀ0.50
R1 = 0.0743
wR2 = 0.1162
1.38/ꢀ1.4
R1 = 0.1158
wR2 = 0.1912
3.87/ꢀ1.03
Final R indexes [all data]
Largest diff. peak/hole / e Åꢀ3
Table 2 Details of data collection and structure refinement for complexes [1aMe]+PF6, [10iPr]PF6.[MePiPr3]PF6 and [10Ph*]PF6.
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