Multidentate 2-pyridyl-phosphine ligands-towards ligand tuning and chirality

Article abstract of DOI:10.1039/c6dt04390a

In the current work a range of multidentate pyridyl-phosphine ligands are synthesised with tuneable electronic and steric character, through the incorporation of a variety of alcohols into (amino)pyridyl-phosphine frameworks. The stoichiometric reactions of compounds of the type (R₂N)_xP(2-py)_3?x (2-py = 2-pyridyl) with alkyl as well as aryl alcohols result in the formation of (alkoxy)pyridyl-phosphines (RO)_xP(2-py)_3?x (R = Me, 2-Bu, Ph). This synthetic procedure also allows the introduction of enantiomerically pure alcohols, like (R)-(?)-2-BuOH and (S)-(+)-2-BuOH, and as such provides a very convenient two-step route to chiral multidentate pyridyl-phosphine ligand sets. Using the bis-amino-phosphine (Et₂N)₂P(2-py), the stepwise introduction of alcohols enables the synthesis of racemic alkoxy-amino-phosphines (R₂N)(RO)P(2-py), as well as alkoxy-phosphines (RO)₂P(2-py) and therefore offers easy access to a library of different pyridyl-phosphine ligands. Coordination studies of the (amino)pyridyl-phosphines and (alkoxy)pyridyl-phosphines with copper(i) reveal that ligands with two N donor atoms form dimeric arrangements, while (PhO)₂P(2-py), in-corporating only one N donor atom, shows completely different coordination behaviour.

Full text of DOI:10.1039/c6dt04390a

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DOI: 10.1039/C6DT04390A
Dalton Transactions
ARTICLE
Multidentate 2-pyridyl-phosphine ligands – towards ligand tuning
and chirality
S. Hanf,a R. García-Rodríguez, a S. Feldmann,a A. D. Bond, a E. Hey-Hawkins*,b and D. S. Wright*,a
Received 00th January 20xx,
Accepted 00th January 20xx
In the current work a range of multidentate pyridyl-phosphine ligands are synthesised with tuneable electronic and steric
character, through the incorporation of a variety of alcohols into (amino)pyridyl-phosphine frameworks. The stoichiometric
reactions of compounds of the type (R2N)xP(2-py)3-x (2-py = 2-pyridyl) with alkyl as well as aryl alcohols result in the formation
of (alkoxy)pyridyl-phosphines (RO)xP(2-py)3-x (R = Me, 2-Bu, Ph). This synthetic procedure also allows the introduction of
enantiomerically pure alcohols, like (R)-(-)-2-BuOH and (S)-(+)-2-BuOH, and as such provides a very convenient two-step
route to chiral multidentate pyridyl-phosphine ligand sets. Using the bis-amino-phosphine (Et2N)2P(2-py), the stepwise
introduction of alcohols enables the synthesis of racemic alkoxy-amino-phosphines (R2N)(RO)P(2-py), as well as alkoxy-
phosphines (RO)2P(2-py) and therefore offers easy access to a library of different pyridyl-phosphine ligands. Coordination
studies of the (amino)pyridyl-phosphines and (alkoxy)pyridyl-phosphines with copper(I) reveal that ligands with two N donor
atoms form dimeric arrangements, while (PhO)2P(2-py), in-corporating only one N donor atom, shows completely different
coordination behaviour.
DOI: 10.1039/x0xx00000x
www.rsc.org/
tripodal counterparts containing Group 13 and 14 metallic or
semi-metallic bridgeheads, like aluminium, have been explored
(Fig. 1c).6–11 However, the high air-sensitivity and reactivity of
Introduction
Tripodal ligands are facially-coordinating, chelate ligands which
possess C3-symmetry, and which have been applied extensively
in coordination, organometallic and bioinorganic chemistry.1 In
particular, the rigid character of these ligands provides a high
degree of stereochemical control in single-site catalysis, due to
a reduced number of competing asymmetric environments in
intermediate octahedral transition metal species.2 In this
context, a large number of studies have focused on the
applications of tris-azolyl borates (Fig. 1a) and (to a lesser
extent) closely related tris-pyridyl derivatives (Fig. 1b) in
catalysis.3–5
the metal-bridged pyridyl compounds limit their applications as
ligands in catalysis and other more robust systems, like 2-
pyridyl-phosphines, have been the centre of interest.12–17
Although the reactivity18–20 and coordination chemistry4,21–
26
of 2-pyridyl-phosphines have been studied in the last three
decades, mixed-ligand pyridyl-phosphines and chiral examples
have been largely overlooked. The introduction of chirality into
pyridyl-phosphines (via chirality at the P atom20 or the
introduction of a chiral substituent) is a logical extension of this
area which can be seen as related to similar developments of
other stereogenic phosphorus ligands which have dominated
the area of asymmetric catalysis, like BINAP,27 DuPhos28–30 and
DIPAMP.31,32 To date, only a few mixed-ligand examples of 2-
pyridyl-phosphines have been reported in the literature, which
are mainly based on phenyl analogues, such as diphenyl(2-
pyridyl)phosphine,
pyridyl)phosphine, PhP(2-py)2.33–43 Other derivatives like
Ph2P(2-py),
and
phenyl-bis(2-
Figure 1. (a) Family of tris-azolyl borates [HB(pz)3]-, (b) neutral tripodal tris-pyridyl ligands
[E(2-py)3] [E = CX (X = H, OR, NH2), N, P, P=O, As] and (c) the aluminium tris-pyridyl
counterparts [RAl(2-py)3]-.
(Me2N)2P(2-py),44 EtPhP(2-py),45 CyP(2-py)2,46 lithiated
47
phosphanylamine
[Li{(2-py)2PNSiMe3}]2
or
(2-
picolyl)phosphane derivatives, like Ph2PPic (Pic
2-py)48–51and Ph2P(NSiMe3)Pic,52,53 have been investigated but
= 2-picolyl, CH2-
As far as tris-2-pyridyl ligands are concerned, until recently
studies have almost exclusively focused on ligands containing
non-metal bridgeheads [E(2-py)3] [2-py = 2-pyridyl, E = CX (X =
H, OR, NH2), N, P, P = O, As]. More recently, isoelectronic
represent rare examples in this field.
Encouraged by the potential for new developments in this
area, our focus in the current paper is to (i) explore synthetic
routes to new multidentate pyridyl-phosphine ligands, (ii) to
investigate the synthetic route(s) which may allow chiral
examples to be obtained and (iii) to examine the coordination
behaviour of the new ligands. For this purpose we have
employed mono- and bis-amino-phosphines of the types
a.Chemistry Department, University of Cambridge, Lensfield Road, CB2 1EW,
Cambridge, UK. E-mail: dsw1000@cam.ac.uk
b.Institute of Inorganic Chemistry, Faculty of Chemistry and Mineralogy, Leipzig
University, Johannisallee 29, 04103 Leipzig, Germany. E-mail: hey@uni-leipzig.de
†
DOI: 10.1039/x0xx00000x. CCDC 1505955-1505962.
Electronic
Supplementary
Informaꢀon
(ESI)
available.
See
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(R2N)xP(2-py)3-x (where R = organic substituent, and x = 1 or 2) which two (LiCl)2 ring units are bridged by two (MVeie2wNA)Prti(c2le-pOnyl)in2e-
as the primary precursors which are readily functionalised by chelated Li+ and two Cl- ions. To the bestDoOfIo: 1u0r.1k0n3o9/wCl6eDdTg0e4,39th0Ae
reactions with alcohols, yielding new (alkoxy)pyridyl- (LiCl)6 core arrangement in [1(LiCl)3∙2THF]2 is unprecedented
phosphines (RO)xP(2-py)3-x (Scheme 1).
among previously reported Li-salt complexes.
a)
b)
Scheme 1. (Amino)pyridyl-phosphines and their post-functionalisation.
Results and Discussion
Synthesis of (amino)pyridyl-phosphines
Figure 2. Structure of (a) [{(Me2N)P(2-py)2}(LiCl)3∙2THF]2 ([1(LiCl)3∙2THF]2) and (b) the
(LiCl)6 core. Hydrogen atoms and carbon atoms of the THF moieties are omitted for
clarity. Displacement ellipsoids are drawn at the 50 % probability level. Selected bond
lengths (Å) and angles (°): P(1)−Cpy(11) 1.847(3), P(1)−Cpy(31) 1.849(3), P(1)−N(2)
Amino-phosphines (R2N)P(2-py)2 and bis-amino-phosphines
(R2N)2P(2-py) are potentially interesting precursors to other
ligand frameworks, since the greater polarity of the P-N
bond,53,54 in contrast to the P-C bond, should facilitate selective
reaction with organic acids. Previously, amino-phosphine
precursors have been employed in the synthesis of alkoxy-
amino-phosphine ligands.55–58 However, only two examples of
bis-amino-pyridyl compounds of the type (R2N)2P(2-py) have
been reported in the literature, (Me2N)2P(2-py)44 and
1.666(3),
Npy(1)–Li(1) 2.044(5), Npy(3)–Li(1) 2.040(6), Cpy(11)–P(1)−Cpy(31) 100.1(2),
Cpy(11)–P(1)−N(2) 104.6(2), Cpy(31)–P(1)−N(2) 104.2(2), P(1)−Cpy(11/21)−Npy(1/3)
115.5(2), Npy(1)−Li(1)−Npy(3) 91.5(2). Blue = N, purple = P, grey = C, green = Cl, teal = Li,
red = O.
Interestingly, the Me2N group of the (Me2N)P(2-py)2 ligand
(Et2N)2P(6-OtBu-2-py).59
Also
some
di-2-
in [
1
(LiCl)3∙2THF]2 is almost planar (sum of RNR angles is 360°)
(without the LiCl
and DFT calculations on the isolated ligand
1
picolylphenylphosphane related amino derivatives have been
described, e. g. [Ph2P(CH2py)(NH2)][N3].60
core) show that the HOMO involves significant electron
donation from the N lone-pair electrons of the Me2N group into
one of the P-C(2-py)σ* orbitals (see ESI, Fig. S1a). This is similar
to the situation found in the tungsten(0) complex [{(Me2N)2P(2-
py)}][W(CO)4], in which one of the Me2N groups is again almost
planar.44
In the current work, the (amino)pyridyl-phosphines
(Me2N)P(2-py)2 (1) and (Et2N)2P(2-py) (2) were obtained from
the reactions of the corresponding phosphorus chlorides
61
(Me2N)PCl2 and (Et2N)2PCl61 (respectively) with in situ
generated 2-pyridylithium at -78 °C in a 1 : 2 or 1 : 1 molar ratio
(Scheme 2).§
The reaction of (Et2N)2PCl and Li(2-py) gives the
(amino)pyridyl-phosphine (Et2N)2P(2-py)
obtained as a pale yellow oil. Looking at the HOMO obtained
from a DFT calculation of (Fig. S1b), a completely different
picture emerges compared to . In this case the electron density
(2), which was
2
1
is mainly located on the P-atom, which may explain the
completely different coordination behaviour of the two ligands,
discussed later.
As part of these studies we also prepared the related ligand
Scheme 2. Synthesis of (a) the amino-phosphine 1 and (b) the bis-amino-phosphine 2.
Ph(Et2N)P(2-py)
substituents, from the reaction of Li(2-py) with Ph(Et2N)PCl62
(Scheme 3). Since has three different substituents, the P is
(3), containing three different organic
The reaction of (Me2N)PCl2 and Li(2-py) produced a mixture
3
of compound
addition to LiCl).§§ Pure samples of [{(Me2N)P(2-
py)2}(LiCl)3∙2THF]2 ([ (LiCl)3∙2THF]2) could be obtained by
crystallisation. Single-crystal X-ray analysis of [ (LiCl)3∙2THF]2
1 and other unidentified P-containing products (in
stereogenic, although it is obtained as a racemic mixture.
1
1
shows that the two (Me2N)P(2-py)2 ligands in the molecular
structure chelate two separate Li+ cations using their two
pyridyl nitrogen atoms (Fig. 2a), with the NMe2 groups of each
ligand remaining uncoordinated. A dimeric structure is formed
which contains a central hexameric (LiCl)6 core (Fig. 2b), in
Scheme 3. Synthesis of the tri-substituted pyridyl-phosphine 3.
2 | J. Name., 2012, 00, 1-3
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Synthesis of (alkoxy)pyridyl-phosphines
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DOI: 10.1039/C6DT04390A
The reaction of the (amino)pyridyl-phosphines [1(LiCl)3∙2THF]2
and
2 with a variety of alcohols has proved to be a
straightforward strategy to the desired (alkoxy)-2-pyridyl-
phosphines (Scheme 4). This synthetic method not only gives
access to a rarely studied ligand class59,63,64 of multidentate
(alkoxy)pyridyl-phosphines, but also allows the stepwise
introduction of two different OR groups (in the case of 2).
Previously, access to these alkoxy species has been limited due
Figure 4. Structure of [{(2-BuO)P(2-py)2}LiCl]2 ([5∙LiCl]2). Hydrogen atoms are omitted for
clarity. Displacement ellipsoids are drawn at the 50 % probability level. Selected bond
lengths (Å) and angles (°): P(1)−Cpy(11) 1.843(6), P(1)−Cpy(21) 1.838(6), P(1)−O(1)
1.618(5), Npy(1)–Li(1) 2.06(1), Npy(2) –Li(1) 2.09(1), Cpy(11)–P(1)−Cpy(21) 97.8(3), Cpy(11)–
P(1)−O(1) 99.5(3), Cpy(21)–P(1)−O(1) 100.9(3), P(1)−Cpy(11)−Npy(1) 113.9(4),
P(1)−Cpy(21)−Npy(2) 115.81(4), Npy(1)−Li(1)−Npy(2) 92.6(4). Blue = N, purple = P, grey = C,
green = Cl, teal = Li, red = O.
to the synthetic challenges involved in the synthesis of the key
§§§
precursors ClxP(2-py)3-x
.
A comparison of the phosphine ligands in the structures of
[
1
(LiCl)3∙2THF]2, [
pyramidal for the alkoxy-substituted ligands, with the sum of
bond angles about the P-atoms being 309 ° in [ (LiCl)3∙2THF]2,
296 ° in [ ∙LiCl]2 and 298 ° in [ ∙LiCl]2 (despite the increase in the
steric congestion in [ ∙LiCl]2 compared to [ (LiCl)3∙2THF]2). This
4∙LiCl]2 and [5∙LiCl]2 shows that they are more
Scheme 4. Synthesis of (alkoxy)pyridyl-phosphines (R = Me, 2-Bu, Ph, py = 2-pyridyl).
1
4
5
The Me2N-group in the amino(pyridyl)-phosphine
5
1
[
1
(LiCl)3∙2THF]2 can easily be replaced by a variety of alcohols.
The reaction of MeOH with crude gives the dimeric LiCl
∙LiCl]2) after crystallisation
trend can be interpreted in terms of VSEPR theory, since there
is less bonding-pair/bonding-pair repulsion in the
(alkoxy)pyridyl-phosphines.
1
complex [{(MeO)P(2-py)2}LiCl]2 ([
(Fig. 3).
4
The reaction of (Et2N)2P(2-py) (2) with different alcohols
allows the stepwise introduction of alkoxy groups, depending
on the nucleophilicity of the alcohol used. In the case of more
nucleophilic MeOH the isolation of the mono-substituted
product (Et2N)(MeO)P(2-py) (
room temperature, since the di-substituted product (MeO)2P(2-
py) ( ) is formed simultaneously even in the 1 : 1 stoichiometric
reaction of
. In situ 31P NMR spectroscopic studies revealed
that after the formation of ca. 30 % of the formation of di-
substituted starts to occur. Di-substituted (MeO)2P(2-py) ( ) is
obtained from the reaction of in MeOH as the solvent. In
contrast, an in situ 31P NMR spectroscopic study of the reaction
of PhOH with in toluene at reflux shows that the 1 : 1 reaction
produces mono-substituted (Et2N)(PhO)P(2-py) ( ) and that the
addition of a second equivalent gives the di-substituted product
(PhO)2P(2-py) ( ) (see ESI, Fig. S35). The new ligands and can
be obtained easily from the preparative scale reactions as pale
This method was readily extended to the more sterically yellow oils.
demanding 2-butanol. The reaction of crude with racemic 2-
butanol results in the formation of (2-BuO)P(2-py)2 ). The
solid-state structure of (Fig. 4) also consists of a dimeric
lithium chloride complex [ ∙LiCl]2, with a similar molecular
structure to [ ∙LiCl]2. This strategy allows the facile introduction
6) did not prove to be possible at
7
2
6
7
7
Figure 3. Structure of [{(MeO)P(2-py)2}LiCl]2 ([4∙LiCl]2). Hydrogen atoms are omitted for
clarity. Displacement ellipsoids are drawn at the 50 % probability level. Selected bond
lengths (Å) and angles (°): P(1)−Cpy(11) 1.842(2), P(1)−Cpy(21) 1.843(2), P(1)−O(1)
1.629(2), Npy(1)–Li(1) 2.105(4), Npy(2)–Li(1) 2.052(5), Cpy(11)–P(1)−Cpy(21) 96.3(1),
Cpy(11)–P(1)−O(1) 99.3(1), Cpy(21)–P(1)−O(1) 100.8(1), P(1)−Cpy(11)−Npy(1) 112.9(2),
P(1)−Cpy(21)−Npy(2) 113.7(2), Npy(1)−Li(1)−Npy(2) 92.0(2). Blue = N, purple = P, grey = C,
green = Cl, teal = Li, red = O.
2
2
8
9
8
9
1
(5
Copper(I) complexes of (amino)pyridyl-phosphines and
(alkoxy)pyridyl-phosphines
5
5
The coordination chemistry of the synthesised phosphines was
studied with CuI. In the past, copper(I) pyridyl-phosphine
complexes have been of interest in catalysis65,66 and because of
their interesting photo-optical properties.67–71
4
of chirality, using the commercially-available (S)- and (R)-
enantiomers of 2-butanol. In situ 31P NMR spectroscopic studies
using the chiral alcohols in place of the racemic 2-butanol
indicate ca. 90 % conversion to the corresponding chiral
Attempts to employ the mono-substituted ligand
(Me2N)P(2-py)2 ([
metal precursors using various reaction conditions were
unsuccessful. However, the reaction of (Et2N)2P(2-py) ( ) with
1
(LiCl)3∙2THF]2) with CuI and other transition
phosphines (5-S and 5-R) under the same conditions.
2
[Cu(MeCN)4]PF6 in MeCN results in the formation of
[(MeCN)Cu{(Et2N)2P(2-py)}]2(PF6)2 (10, Scheme 5). Similarly to
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N
py(1)−Cu(1)
2.072(2), N(3)−Cu(1) 2.334(3), P(1)−Cpy(11)−Npy(1)
113.2(2),
previously reported diamagnetic iron(II) and copper(I)
complexes of P(2-py)3 and P(6-Me-2-py)3, the P-resonance of
the (Et2N)2P(2-py) ligand in 10 is shifted upfield in the 31P{1H}
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P(1)−Cu(1’)−Npy(1’) 118.74(4), P(1)−Cu(1’)−N(3’) 118.77(6). Blue = N, purple = P, grey = C,
DOI: 10.1039/C6DT04390A
turquoise = Cu.
NMR spectrum with respect to the uncoordinated ligand 2 17
.
The reaction of the (alkoxy)pyridyl-phosphine [4∙LiCl]2 with
The different coordination behaviour of 1 compared to 2 is
[Cu(MeCN)4]PF6 in THF resulted in the formation of a few
crystals of [ClCu{(MeO)P(2-py)2}]2∙MeOH (11∙MeOH, Scheme
5).§§§§ The transition metal complex, which is the first example
of a metal complex of an alkoxy-(bis-pyridyl) ligand, is very
similar to 10 and again consists of a centrosymmetric dimer, in
which each CuI atom is chelated by the two pyridyl-N atoms of
analogous to di-2-picolylphenylphosphane ligands, which have
been investigated by electron density studies.72
one of the two ligands
4
and by the P-bridgehead atom of the
are not
other ligand (Fig. 6). The MeO groups of the ligands
4
coordinated to CuI, as might be expected on the basis of hard-
soft concepts.
Figure 6. Structure of [ClCu{(MeO)2P(2-py)}]2∙MeOH (11∙MeOH). Hydrogen atoms and
the MeOH molecule are omitted for clarity. Displacement ellipsoids are drawn at the
50 % probability level. Selected bond lengths (Å) and angles (°): P(1)−Cpy(11) 1.833(3),
P(1)−Cpy(21) 1.839(2), P(1)−O(1) 1.616(2), P(1)−Cu(1) 3.2108(7), P(1)−Cu(1’) 2.1641(8),
Npy(1)−Cu(1) 2.078(2), Npy(2)−Cu(1) 2.072(3), P(1)−Cpy(11)−Npy(1) 115.2(2),
P(1)−Cpy(21)−Npy(2) 115.7(2), P(1)−Cu(1’)−Npy(1’) 118.78(7), P(1)−Cu(1’)−Npy(2’)
119.76(7). Blue = N, purple = P, grey = C, green = Cl, red = O, turquoise = Cu.
The reaction of (Et2N)(PhO)P(2-py) (8) with [Cu(MeCN)4]PF6
Scheme 5. Synthesis of the CuI pyridyl-phosphine complexes (10 - 13).
in MeCN yielded crystals of [(MeCN)Cu{(Et2N)(PhO)P(2-
py)}]2(PF6)2 (12, Fig. 7). Again as observed for 10, the 31P{1H}
singlet for 12 is broadened and shifted upfield relative to the
free ligand. In the dimeric structure, the CuI atoms are chelated
by the N-atoms of the Et2N and 2-py groups of one of the ligands
The solid-state structure of 10 (Figure 5), determined by
single-crystal X-ray crystallography, is that of a centrosymmetric
dimer. In 10 one of the NEt2 groups of each of the ligands 2 does
not coordinate CuI, with each CuI ion being chelated by the N-
atoms of the remaining NEt2 group and the 2-py group of each
ligand. The dimeric structure comes about by the formation of
8
as well as the P-bridgehead of the second ligand molecule. The
PhO-groups of both ligand molecules remain uncoordinated.
The structure is therefore very similar to that seen for 10 and
11∙MeOH.
inter-monomer Cu-P bonds to the bridgehead P-atom of 2.
Figure 7. Dimeric structure of [(MeCN)Cu{(Et2N)(PhO)P(2-py)}]2(PF6)2 (12). Hydrogen
atoms as well as the PF6- counterions are omitted for clarity. Displacement ellipsoids are
drawn at the 50 % probability level. Selected bond lengths (Å) and angles (°): P(1)−Cpy(11)
1.824(2), P(1)−N(2) 1.676(2), P(1)−O(1) 1.636(1), P(1)−Cu(1) 2.9613(6), P(1)−Cu(1’)
2.1974(6), Npy(1)−Cu(1) 2.055(2), N(2)−Cu(1) 2.543(2), P(1)−Cpy(11)−Npy(1) 112.9(1),
Figure 5 Dimeric structure of [(MeCN)Cu{(Et2N)2P(2-py)}]2(PF6)2 (10). Hydrogen atoms as
well as the PF6- counterions are omitted for clarity. Displacement ellipsoids are drawn at
the 50 % probability level. Selected bond lengths (Å) and angles (°): P(1)−Cpy(11) 1.833(3),
P(1)−N(2) 1.658(3), P(1)−N(3) 1.740(2), P(1)−Cu(1) 2.9234(8), P(1)−Cu(1’) 2.2137(8),
4 | J. Name., 2012, 00, 1-3
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P(1)−Cu(1’)−Npy(1’) 119.60(5), P(1)−Cu(1’)−N(2’) 112.82(4). Blue = N, purple = P, grey = C,
red = O, turquoise = Cu.
31P{1H} NMR spectrum. This signal splits into a doublet (1JPH
=
View Article Online
597.2 Hz) in the 31P spectrum, suggesting the formation of a P-
DOI: 10.1039/C6DT04390A
H containing species. Further confirmation of this comes from
X-ray crystallography of crystals of this new species. This shows
that the new complex is [{OP(O)(H)(2-py)}Cu2{(PhO)2P(2-
Ligands 2, [4∙LiCl]2 and 8, which contain at least two nitrogen
atoms, produce similar structural arrangements with CuI.
Interestingly, however, when only one nitrogen atom is present
py)}2]2(PF6)2∙2THF (14∙2THF), which contains (PhO)2P(2-py) (
and [OP(O)(H)(2-py)]- ligands, the later ligand apparently
resulting from hydrolysis of by adventitious water. The
9)
for coordination to the soft CuI centre, as in (PhO)2P(2-py) (
completely different type of complex is formed. The reaction of
with [Cu(MeCN)4]PF6 in MeCN under reflux conditions gives
9), a
9
9
formation of the [OP(O)(H)(2-py)]- ligand accounts for the
observation of a P-H resonance in the 31P{1H} NMR spectrum.
The complicated centrosymmetric structural arrangement of
14∙2THF contains a central Cu2P2O4 ring unit. The four CuI ions
have pseudo-tetrahedral geometries, and are coordinated by
the [OP(O)(H)(2-py)]- ligands (using the two O- and the pyridyl-
[(MeCN)Cu2{(PhO)2P(2-py)}3](PF6)2∙3THF (13∙3THF, Scheme 5,
Fig. 8).
N atoms) and by the ligand 9 (using one of the pyridyl-N and the
bridgehead P-atom) (Fig. 9). Compound 14∙2THF is not
thermally stable. In situ 31P NMR spectroscopic studies of a
solution of crystals of 14∙2THF dissolved in MeCN shows that
the [OP(O)(H)(2-py)]- ligand completely decomposes after reflux
(72 h), leaving only the resonance for (PhO)2P(2-py) (9). This
observation explains why 13∙3THF is formed exclusively in the
reaction at reflux, in the absence of the hydrolysis product
14∙2THF.
Figure 8. Structure of [(MeCN)Cu2{(PhO)2P(2-py)}3](PF6)2∙3THF (13∙3THF) (left) and the
a)
-
space filling diagram (right). Hydrogen atoms, one PF6 counterion as well as the THF
molecules are omitted for clarity. Displacement ellipsoids are drawn at the 50 %
probability level. Selected bond lengths (Å) and angles (°): P−Cpy 1.816(3)-1.827(3), P−O
1.601(3)-1.614(2), P−Cu(1) 2.2594(9)-2.2924(8), P−Cu(2) 3.062(1)-3.180(1), Npy−Cu(2)
1.983(2)-2.034(3), Cu(2)–F(2) 2.90(1), P−Cpy−Npy 111.2(2)-114.3(3). Blue = N, purple = P,
grey = C, green = F, red = O, turquoise = Cu.
In the binuclear complex [(MeCN)Cu2{(PhO)2P(2-
py)}3](PF6)2∙3THF (13∙3THF) one of the CuI centers [Cu(2)] is
b)
coordinated by three pyridyl-N atoms of three separate ligands
-
9
, as well being loosely coordinated by the F-atom of a PF6
anion (Cu•••F 2.90(1) Å) (the other of which, balancing the +2
charge, is not coordinated). Similar Cu•••F interactions have
been seen in two-dimensional CuII coordination polymers of the
type {[Cu(PF6)(4,4′-bpy)2(MeOH)]∙PF6∙3MeOH}n, in which Cu•••F
distances of 2.306(3)-2.614(3) Å have been observed.73 The
remaining CuI center in 13∙3THF is bonded to the three P-atoms
of the three ligands
9 and to a MeCN molecule, resulting in a
Figure 9. (a) Schematic structure (R = OPh) and (b) solid-state structure of [{OP(O)(H)(2-
py)}Cu2{(PhO)2P(2-py)}2]2(PF6)2∙2THF (14∙2THF) Hydrogen atoms, PF6- counterions as well
as THF molecules are omitted for clarity. Displacement ellipsoids are drawn at the 50 %
probability level. Selected bond lengths (Å) and angles (°): P−Cpy 1.815(6)-1.824(6),
P−OPh 1.614(4)-1.631(4), P(3)−O 1.474(4)-1.490(4), P(1’)−Cu(2) 2.128(2), P(2’)−Cu(1)
2.148(2), N(1)−Cu(1)−N(3) 111.2(2), O(5)−Cu(2’)−O(6’) 100.5(2). Blue = N, purple = P, grey
= C, red = O, turquoise = Cu.
pseudo-tetrahedral geometry. The bridging of the two CuI
centers in 13∙3THF results in a short Cu•••Cu distance of
2.9431(7) Å. Similar Cu•••Cu distances were observed in
dinuclear
CuI
complexes
of
Ph2P(2-pypz)
[(2-
diphenylphosphino-6-pyrazol-1-yl)pyridine]74 and Ph2P(2-py)68
but cannot be considered as significant metallophilic
interactions. As seen before in the structures of 11 and 12, the
PhO groups of
9
are not bonded to CuI. Again this is due to the
Conclusions
hardness of the O atoms relative to the soft N- and P-ligand set.
Once more the 31P{1H} NMR shift of 13∙3THF is shifted upfield
and the signal is broadened in comparison with the free ligand
In the current work we have shown that the 2-pyridyl-
phosphine ligand set can be extensively elaborated upon using
a simple set of synthetic approaches. The alkoxy-phosphines
(RO)xP(2-py)3-x are easily derived from amino-phosphines
(R2N)xP(2-py)3-x by direct reactions with alcohols. In addition,
step-wise reaction of alcohols with the amino-phosphines can
be used to obtain multidentate alkoxy-amino phosphines
9
.
When the reaction of
9 with [Cu(MeCN)4]PF6 in MeCN was
carried out at room temperature (instead of at reflux), in
addition to the broad signal at δ = 120.1 ppm (in CD3CN) for 13
a sharp singlet at δ = 21.6 ppm was repeatedly observed in the
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(R2N)(RO)P(2-py) (containing three different substituents). We this dark red mixture, (Me2N)PCl2 (0.92 mL, 1.17 g, 8 mmol) in
View Article Online
DOI: 10.1039/C6DT04390A
have also investigated the coordination chemistry of a range of 15 mL of diethyl ether was added. After the addition, the
these new ligand systems for the first time, showing that both suspension was allowed to warm to room temperature
the pyridyl-N and bridgehead-P atoms can be involved in overnight. The formed pale orange solution, containing a brown
coordination to the soft CuI centres. Ligands of this type precipitate, was filtered and the solid dried in vacuo. The solid
containing two or more N-donor atoms show completely consists of a mixture of
different coordination behaviour to those in which only one N- % product, 14 % side products according to 31P{1H} NMR) as well
donor is present. as LiCl (m(total) = 1.70 g). Layering of a saturated THF solution
1 and other P-containing products (86
The synthetic approach that we have developed for easy with n-hexane resulted in the crystallisation of [{(Me2N)P(2-
modification of the 2-pyridyl-phosphine ligand framework py)2}(LiCl)3∙2THF]2. 1H NMR (d8-THF), δ = 8.71 - 8.67 (2H, m, H6),
provides the potential means for the introduction of chirality, 7.72 - 7.65 (4H, m, H3,4), 7,22 - 7.16 (2H, m, H5), 3.69 - 3.63 (8H,
by creating stereogenic P-bridgeheads or through the m, THF, OCH2), 2.82 (6H, d, JPH = 9.0, CH3), 1.85 - 1.78 (8H, m,
introduction of chiral alkoxide groups. Transition metal THF, CH2). 31P{1H} NMR (d8-THF), δ = 60.1 (s). 13C{1H} NMR (d8-
complexes of this type could find versatile applications in THF), δ = 165.7 (d, JCP = 1.9, C2), 150.3 (d, JCP = 10.4, C6), 135.5
asymmetric catalytic reactions.
(d, JCP = 2.1, C3/4), 126.5 (d, JCP = 17.7, C3/4), 122.3 (s, C5), 68.0
(s, THF, OCH2), 43.0 (d, JCP = 14.5, CH3), 26.2 (s, THF, CH2). 7Li{1H}
NMR (d8-THF), δ = 0.35 (s). Elemental analysis, calcd. for
[{(Me2N)P(2-py)2}(LiCl)3∙2THF]2, C 47.9, H 6.0, N 8.4; found C
46.8, H 6.1, N 7.9.
Experimental Section
All experiments were carried out on a Schlenk-line under N2
atmosphere or in an N2-filled glove box (Saffron type α).
Toluene, diethyl ether n-hexane and THF were dried under
nitrogen over sodium or sodium/benzophenone, respectively,
whereas acetonitrile, methanol and dichloromethane were
dried over calcium hydride. 2-Bromopyridine and phosphorus
trichloride were purified by distillation prior to use. All other
reagents were used as purchased from the supplier.
(Me2N)PCl259 and (Et2N)2PCl61 and Ph(Et2N)PCl62 were prepared
according to literature procedures. H, 13C{1H}, Li{1H} , 31P{1H}
and 31P NMR spectra were recorded on a Bruker Avance 400
QNP or Bruker Avance 500 MHz cryo spectrometer. 1H, 13C{1H},
7Li{1H} , 31P{1H} and 31P NMR spectra at 298 K were measured at
400.14 MHz, 100.63 MHz, 161.98 MHz and 155.51 MHz,
respectively, unless noted otherwise. δ and J values are given in
ppm and Hz, respectively. All spectra were recorded in CDCl3,
CD3CN, d8-THF, CD3COCD3 or d8-toluene with SiMe4 (1H) and
H3PO4 (31P, 85% in D2O) as external standards. Unambiguous
assignments of NMR resonances were made on the basis of 2D
Synthesis of (Et2N)2P(2-py) (2). 2-Bromopyridine (1.9 mL, 20
mmol) in 25 mL of diethyl ether was added dropwise over a
period of 30 min to a solution of nBuLi (12.5 mL, 20 mmol, 1.6 M
in n-hexane) at -78 °C. The resulting dark orange solution was
stirred for 2 h at -78 °C. (Et2N)2PCl (4.20 mL, 20 mmol) was
added dropwise, resulting in a dark brown mixture. After
stirring overnight (over which time the reaction reached RT), a
dark-green solution with a precipitate was formed. This solution
was then filtered to remove the solid. The solvent was removed
in vacuo and distillation of the resulting dark brown oil under
reduced pressure (b. p. 82 °C, 0.1 mbar) gave a yellow oil. Yield:
1
7
1
2.87 g, 11.30 mmol, 57 %. H NMR (CDCl3), δ = 8.70 - 8.68 (1H,
m, H6), 7.61 - 7.56 (1H, m, H4), 7.56 - 7.51 (1H, m, H3), 7.06 -
7.02 (1H, m, H5), 3.16 - 3.07 (8H, m, CH2), 1.14 (12H, t, JHH = 7.1,
CH3). 31P{1H} NMR (CDCl3), δ = 93.9 (s). 13C{1H} NMR (CDCl3), δ =
165.9 (d, JCP = 16.3, C2), 150.1 (d, JCP = 7.6, C6), 135.0 (s, C4),
126.5 (d, JCP = 22.3, C3), 121.1 (s, C5), 43.5 (d, JCP = 16.3, CH2),
14.5 (d, JCP = 2.3, CH3). Elemental analysis, calcd. for (Et2N)2P(2-
py), C 61.6, H 9.6, N 16.6; found C 61.7, H 9.8, N 16.1. HR-MS
(ESI, +, DCM): m/z: 254.1772, calcd. 254.1781 (3.4 ppm error),
[M+].
NMR experiments (1H-1H COSY, H-13C HSQC and H-13C HMBC
experiments). Scheme 6 depicts the labelling scheme for NMR
assignments used in the experimental section. Elemental
analyses were obtained using a Perkin Elmer 240 Elemental
Analyser.
1
1
Synthesis of (Et2N)PhP(2-py) (3). 2-Bromopyridine (1.90 mL, 20
mmol) in 25 mL of diethyl ether was added dropwise over a
period of 40 min to an nBuLi solution (12.5 mL, 20 mmol, 1.6 M
in n-hexane) at -78 °C. The dark red mixture was stirred for 3 h
and then (Et2N)PhPCl in 5 mL of diethyl ether was added
dropwise. The resulting dark brown mixture was warmed up to
room temperature overnight, resulting in an orange solution
with a pale brown precipitate. After the mixture was filtered
over Celite, the solvent was removed affording a crimson oil (m
= 2.84 g). The dark red oil was distilled under reduced pressure
Scheme 6. Atom labelling scheme used in the NMR studies for the pyridyl-phosphine
to afford
3
as yellow oil. Yield: 1.05 g, 4.1 mmol, 20 %. 1H NMR
compounds.
(500.20 MHz, CDCl3), δ = 8.71 (1H, d, JHH = 4.7, H6), 7.67 - 7.62
(1H, m, H4), 7.54 - 7.51 (1H, m, H3), 7.45 - 7.41 (2H, m, Ph-H-
ortho), 7.37 - 7.29 (3H, m, Ph-H-meta, para), 7.18 - 7.14 (1H, m,
H5), 3.21 - 3.08 (4H, m, CH2), 0.99 (6H, t, JHH = 7.1, CH3). 31P{1H}
NMR (CDCl3), δ = 59.7 (s). 13C{1H} NMR (125.78 MHz, CDCl3), δ =
165.8 (d, JCP = 16.3, C2), 149.9 (d, JCP = 11.0, C6), 139.3 (d, JCP
Synthesis
of
(Me2N)P(2-py)2
([1(LiCl)3∙2THF]2).
2-
Bromopyridine (1.53 mL, 2.53 g, 16 mmol) in 20 mL of diethyl
ether was added dropwise over a period of 30 min to a solution
of nBuLi (10.00 mL, 16 mmol, 1.6 M in n-hexane) at -78 °C. The
resulting dark orange solution was stirred for 3 h at -78 °C. To
6 | J. Name., 2012, 00, 1-3
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=13.8, Ph-Cq), 135.2 (d, JCP = 2.2, C4), 132.3 (d, JCP = 20.1, Ph- yield according to 31P{1H} NMR spectroscopy. 1H NMR (d8-tol), δ
View Article Online
DOI: 10.1039/C6DT04390A
ortho), 128.3 (s, Ph-meta, para), 128.0 (d, JCP = 6.2, Ph-meta, = 8.66 - 8.61 (2H, m, H6), 7.69 - 7.63 (2H, m, H3), 7.10 - 7.04 (2H,
para), 126.4 (d, JCP = 18.1, C3), 121.7 (s, C5), 44.6 (d, JCP = 15.4, m, H4), 6.63 - 6.56 (2H, m, H5), 4.11 - 4.01 (1H, m, OCH), 1.82 -
CH2), 14.4 (d, JCP = 3.0, CH3). Elemental analysis, calcd for 1.68 (1H, m, CH2), 1.58 - 1.50 (1H, m, CH2), 1.28 (3H, d, JHH = 6.3,
(Et2N)PhP(2-py), C 69.8, H 7.4, N 10.9; found C 70.3, H 7.5, N OCHCH3), 0.88 (3H, t, JHH = 7.4, CH2CH3). 31P{1H} NMR (d8-tol), δ
10.9. MS (ESI, +, MeCN): m/z: 259.1362, calcd. 254.1359 (1.18 = 92.8 (s).
ppm error), [M+].
Synthesis of (MeO)2P(2-py) (7). A mixture of 2 (0.666 g, 2.63
Synthesis of (MeO)P(2-py)2 ([4∙LiCl]2). The crude precipitate of mmol) and 30 mL MeOH was heated overnight at 50 °C. The
(Me2N)P(2-py)2∙LiCl + LiCl (1.00 g, 3.18 mmol) was stirred in mixture was dried under vacuum resulting in a clear pale yellow
1
MeOH (40 mL) overnight resulting in a clear orange solution. oil. Yield: 0.35 g, 2.05 mmol, 73 %. H NMR (CDCl3), δ = 8.81 -
After the solvent was removed in vacuo the product was 8.78 (1H, m, H6), 7.77 - 7.69 (2H, m, H3,4), 7.28 - 7.23 (1H, m,
obtained as brown oil, which could be crystallised as H5), 3.65 (6H, d, JPH = 10.6, Me). 31P{1H} NMR (CDCl3), δ = 150.1
[{(MeO)P(2-py)2}LiCl]2 from
a
concentrated THF solution (s). 13C{1H} NMR (CDCl3), δ = 163.7 (d, JCP = 6.0, C2), 150.3 (d, JCP
1
at -14 °C. Crystalline yield: 0.22 g, 0.84 mmol, 27 %. H NMR = 11.4, C6), 135.6 (s, C4), 125.1 (d, JCP = 15.9, C3), 123.9 (s, C5),
(CDCl3), δ = 8.78 (2H, d, JHH = 4.8 , H6), 7.68 - 7.64 (4H, m, H3,4), 53.8 (d, JCP = 9.2, CH3). Elemental analysis, calcd. for (MeO)2P(2-
7.23 - 7.18 (2H, m, H5), 3.89 (3H, d, JPH = 13.5, CH3). 31P{1H} NMR py), C 49.1, H 5.9, N 8.2; found C 49.6, H 6.0, N 8.4. HR-MS (ESI,
(CDCl3), δ = 99.5 (s). 13C{1H} NMR (CDCl3), δ = 164.3 (d, JCP = 8.3, +, MeCN): m/z: 172.0518, calcd. 172.0522 (-2.52 ppm error),
C2), 150.6 (d, JCP = 10.4, C6), 136.1 (d, JCP = 4.1, C4), 125.0 (d, JCP [M+].
7
= 21.1, C3), 123.4 (s, C5), 58.2 (d, JCP = 21.2, CH3). Li{1H} NMR Synthesis of (Et2N)(PhO)P(2-py) (8). 2 (0.860 g, 3.40 mmol) and
(CDCl3), δ = 2.33 (s). Elemental analysis, calcd. for [{(MeO)P(2- PhOH (0.319 g, 3.40 mmol) were brought to reflux in toluene
py)2}LiCl]2, C 43.6, H 3.7, N 9.3; found C 44.7, H 3.9, N 9.9.
(20 mL) overnight. After the solvent was removed in vacuo the
Synthesis of (2-BuO)P(2-py)2 ([5∙LiCl]2). The crude compound product was obtained as yellow oil. Yield: 0.81 g, 2.93 mmol,
1
(Me2N)P(2-py)2∙LiCl + LiCl (1,36 g, 4.30 mmol) and 2 eq of 86 %. H NMR (CDCl3), δ = 8.81 - 8.79 (1H, m, H6), 7.96 - 7.92
racemic 2-butanol (0.79 mL, 8.7 mol) were heated overnight at (1H, m, H3), 7.76 (1H, tt, JHH = 7.6, 2.0, H4), 7.36 - 7.30 (2H, m,
90 °C in 15 mL of toluene. The mixture was filtered over Celite Ph-H-meta), 7.28 - 7.25 (1H, m, H5), 7.17 - 7.13 (m, 2H, Ph-H-
and the solvent was removed, resulting in 0.79 g of a brown oil ortho), 7.09 - 7.04 (1H, m, Ph-H-para), 3.22 - 3.05 (4H, m, CH2),
with a purity of 80 % according to 31P{1H} NMR spectroscopy. 1.00 (6H, t, JHH = 7.3, CH3). 31P{1H} NMR (CDCl3), δ = 120.2 (s).
Colourless single-crystals of [{(2-BuO)P(2-py)2}LiCl]2 could be 13C{1H} NMR (CDCl3), δ = 164.7 (d, JCP = 11.6, C2), 156.7 (d, JCP
=
obtained from layering a saturated THF solution with n-hexane. 8.3, Ph-Cq), 150.2 (d, JCP = 13.2, C6), 135.9 (s, C4), 129.6 (s, Ph-
1
Crystalline yield: 0.070 g, 0.23 mmol, 5 %. H NMR (CDCl3), δ = meta), 126.1 (d, JCP = 14.7, C3), 123.2 (s, C5), 122.4 (d, JCP = 1.6,
8.83 (2H, d, JHH = 5, H6), 7.76 - 7.67 (4H, m, H3,4), 7.25 - 7.20 Ph-H-para), 119.9 (d, JCP = 9.4, Ph-ortho), 43.2 (s, CH2), 15.0 (d,
(2H, m, H5), 4.24 - 4.14 (1H, m, OCH), 1.93 - 1.81 (1H, m, CH2), JCP = 3.8, CH3). Elemental analysis, calcd. for (Et2N)(PhO)P(2-py),
1.78 - 1.65 (1H, m, CH2), 1.41 (3H, d, JHH = 6.4, OCHCH3), 0.98 C 65.7, H 7.0, N 10.2; found C 65.3, H 7.2, N 10.1. HR-MS (ESI, +,
(3H, t, JHH = 7.5, CH2CH3). 31P{1H} NMR (CDCl3), δ = 88.1 (s). MeCN): m/z: 275.1310, calcd. 275.1308 (0.95 ppm error), [M+].
13C{1H} NMR (CDCl3), δ = 164.9 (d (br), JCP = 35.8, C2), 150.8 (d, Synthesis of (PhO)2P(2-py) (9). A mixture of
JCP = 10.1, C6), 136.5 (d, JCP = 4.0, C3/4), 124.9 - 124.5 (m, C3/4), mmol) and two equivalents of PhOH (0.622 g, 6.61 mmol) were
123.4 (d, JCP = 2.5, C5), 80.9 (d, JCP = 20.8 , OCH), 31.1 (d, JCP brought to reflux for 41 h in toluene (18 mL). After the solvent
2 (0.837 g, 3.30
=
7
5.6, CH2), 21.8 (d, JCP = 5.6, OCHCH3), 10.1 (s, CH2CH3). Li{1H} was removed in vacuo the resulting pale yellow oil was purified
NMR (CDCl3), δ = 2.51 (s). Elemental analysis, calcd. for [{(2- by vacuum distillation and then heated at 100 °C (to remove the
BuO)P(2-py)2}LiCl]2, C 55.6, H 5.7, N 9.3; found C 55.8, H 5.8, N excess PhOH) for 2 h to afford
9 in 96 % purity (according to
1
9.0.
31P{1H} NMR spectroscopy). Yield: 0.43 g, 1.46 mmol, 44 %. H
Synthesis of
(
S)-(2-BuO)P(2-py)2 ([5-
S
∙LiCl]2). Crystals of NMR (CD3CN), δ = 8.88 (1H, d, JHH = 4.7, H6), 7.98 - 7.94 (1H, m,
[{(Me2N)P(2-py)2}(LiCl)3∙2THF]2 (0.017g, 0.034 mmol) were H3), 7.86 (1H, tt, JHH = 7.7, 16, H4), 7.47 - 7.42 (1H, m, H5), 7.37
reacted with (S)-(+)-2-Butanol (6.3 μL, 0.068 mmol) in 0.6 mL of - 7.31 (4H, m, Ph-H-meta), 7.17 - 7.12 (4H, m, Ph-H-ortho, para).
d8-toluene in a Young’s NMR tube. The mixture was heated 31P{1H} NMR (CD3CN), δ = 142.8 (s). 13C{1H} NMR ( CD3CN), δ =
overnight at 85 °C. The phosphine 5-S was obtained in 91 % yield 162.5 (d, JCP = 5.0, C2), 155.0 (d, JCP = 4.2, Ph-Cq), 150.1 (d, JCP =
1
according to 31P{1H} NMR spectroscopy. H NMR (d8-tol), δ = 15.8, C6), 136.3 (s, C4), 129.7 (s, Ph-meta), 125.0 (s, C5), 124.6
8.66 - 8.57 (2H, m, H6), 7.69 - 7.63 (2H, m, H3), 7.10 - 7.04 (2H, (d, JCP = 12.9, C3), 124.0 (d, JCP = 1.1, Ph-ortho/para), 120.1 (d,
m, H4), 6.63 - 6.56 (2H, m, H5), 4.11 - 4.01 (1H, m, OCH), 1.79 - JCP = 7.6, Ph-ortho/para). Elemental analysis, calcd. for
1.69 (1H, m, CH2), 1.59 - 1.52 (1H, m, CH2), 1.28 (3H, d, JHH = 6.3, (PhO)2P(2-py), C 69.2, H 4.8, N 4.7; found C 69.6, H 5.0, N 4.5.
OCHCH3), 0.88 (3H, t, JHH = 3.7, CH2CH3). 31P{1H} NMR (d8-tol), δ HR-MS (ESI, +, MeCN): m/z: 296.0842, calcd. 296.0835 (2.25
= 93.1 (s).
ppm error), [M+].
Synthesis of
(
R)-(2-BuO)P(2-py)2 ([5-
R∙LiCl]2). Crystals of Synthesis of [(MeCN)Cu{(Et2N)2P(2-py)}]2(PF6)2 (10). 2 (0.01g,
[{(Me2N)P(2-py)2}(LiCl)3∙2THF]2 (0.015g, 0.030 mmol) were 0.4 mmol) and [Cu(MeCN)4]PF6 (0.15g, 0.4 mmol) were reacted
reacted with (R)-(-)-2-Butanol (5.5 μL, 0.060 mmol) in 0.6 ml of in MeCN (20 mL). The bright yellow mixture was stirred
d8-toluene in a Young’s NMR tube. The mixture was heated overnight and the solvent was removed completely under
overnight at 85 °C. The phosphine 5-R was obtained in 94 % vacuum. Colourless crystals could be grown from layering a
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saturated DCM solution with n-hexane. Crystalline yield: 74 mg, MeCN was stirred overnight at room temperature, resulting in
View Article Online
1
DOI: 10.1039/C6DT04390A
0.074 mmol, 19 %. H NMR (CD3COCD3), δ 8.75 (1H, s (br), py- a pale yellow solution. After the solvent was removed colourless
H), 8.10 - 7.31 (3H, m, py-H), 3.25 - 2.88 (8H, m, CH2), 1.99 (3H, crystals of 14∙2THF could be grown from a saturated THF
s, MeCN), 1.13 (12H, t, JHH = 6.7, CH3). 31P{1H} NMR (CD3COCD3), solution at -14 °C. Crystalline yield: 0.048 g, 4 %. In the following
δ = 84.0 (s, br), -144.6 (sep, JPF = 707.1, PF6). 13C{1H} NMR NMR assignment the ligand
spectrum could not be obtained due to extensive line [OP(O)(H)(2-py)]- will be denoted as L2. H NMR (CD3CN), δ =
broadening. Elemental analysis, calcd. for 8.84 (1H, d, JHH= 4.7, py-H, L2), 8.81 (2H, d, JHH= 4.2, py-H, L1),
[(MeCN)Cu{(Et2N)2P(2-py)}]2(PF6)2, C 35.8, H 5.4, N 11.1; found 8.02 - 7.89 (6H, m, py-H, L1, L2), 7.77 (1H, d, JPH= 597.2, PH, L2),
C 35.1, H 5.3, N 10.6. 7.65 - 7.60 (1H, m, py-H, L2), 7.56 - 7.51 (2H, m, L1), 7.43 - 7.35
Synthesis of [ClCu{(MeO)P(2-py)2}]2∙MeOH (11∙MeOH). (8H, m, Ph-H, L1), 7.26 -7.17 (12H, m, Ph-H, L1). 31P{1H} NMR
0.091 g [{(MeO)P(2-py)2}LiCl]2 ([ ∙LiCl]2) (0.35 mmol) and (CD3CN), δ = 119.8 (s, br, L1), 21.6 (s, L2), -144.6 (sep, JPF = 706.5,
9 will be referred to as L1 whereas
1
4
[Cu(MeCN)4]PF6 (0.13 g, 0.35 mmol) were brought to reflux in PF6). 31P NMR (CD3CN), δ = 119.8 (s, br, L1), 21.6 (d, JPH= 597.2,
15 mL THF. After the solvent was removed MeOH was added PH, L2), -144.6 (sep, JPF = 706.5, PF6). 13C{1H} NMR spectrum
and the mixture was filtered over Celite. A few colourless could not be obtained due to extensive line broadening.
crystals of 11∙MeOH could be grown from a saturated MeOH Elemental analysis, calcd. for [{OP(O)(H)(2-py)}Cu2{(PhO)2P(2-
solution at -14 °C.
py)}2]2(PF6)2, C 46.6, H 3.3, N 4.2; found C 46.5, H 3.7, N 4.1.
Synthesis of [(MeCN)Cu{(Et2N)(PhO)P(2-py)}]2(PF6)2 (12). 8 Computational Details
(0.248 g, 0.9 mmol) and [Cu(MeCN)4]PF6 (0.337g, 0.9 mmol) in
Geometry optimisation of the ligand sets
1 and 2 were carried
MeCN (15 mL) were brought to reflux for 2 h. The yellow
solution was filtered over Celite and the solvent was removed
under reduced pressure, resulting in a yellow oil. Colourless
crystals could be obtained from a saturated DCM solution
at -14 °C after two days. Crystalline yield: 0.05 g, 0.048 mmol, 5
%. 1H NMR (CD3CN), δ = 8.77 - 8.73 (1H, m, H6), 8.01 - 7.94 (1H,
m, H3), 7.94 - 7.86 (1H, m, H4), 7.47 - 7.42 (1H, m, H5), 7.42 -
7.36 (2H, m, Ph-H), 7.20 - 7.13 (3H, m, Ph-H), 3.22 - 3.07 (4H, m,
CH2), 1.96 (MeCN solvent residual signal partially overlaps with
the signal of the coordinated MeCN molecules), 0.98 (6H, t, JHH
= 7.1, CH3). 31P{1H} NMR (CD3CN), δ = 107.8 (s, br), -144.6 (sep,
JPF = 705.9, PF6). 13C{1H} NMR (CD3CN), δ = 160.3 (d, JCP = 76.5,
C2), 155.4 (s, Ph-Cq), 151.3 (d, JCP = 17.3, C6), 137.5 (s, C4), 130.5
(s, Ph), 126.6 (d, JCP = 18, C3), 125.5 (s, C5), 124.9 (s, Ph), 121.9
(d, JCP = 6.2, Ph), 118.2 (s, MeCN), 42.8 (d, JCP = 11.0, CH2), 14.7
(s, CH3), 0.76 (s, MeCN). Elemental analysis, calcd. for
[(MeCN)Cu{(Et2N)(PhO)P(2-py)}]2(PF6)2, C 39.0, H 4.3, N 8.0;
found C 38.8, H 4.3, N 8.0.
out using the Gaussian-Program package.75 The optimised
structures were obtained employing the B3LYP functional76–78
in conjunction with a 6-31g** basis set.79,80 Frequency
calculations of the optimised structures were carried out in
order to proof the absence of imaginary frequencies. Molecular
orbitals were visualised using the program VMD - Visual
Molecular Dynamics.81
Single-crystal X-ray crystallography
Single-crystal X-ray diffraction was carried out at 180(2) K on a
Bruker D8-QUEST PHOTON-100 diffractometer using an
Incoatec IμS Cu microsource (λ = 1.5418 Å). Data collection and
processing were carried out using the APEX2/APEX3 packages.
Structures were solved using SHELXT82 and refined using
SHELXL-2014.83 Details of the refinements are provided in the
ESI (Table S1 and S2). CCDC 1505955-1505962.
Acknowledgements
Synthesis
of
[(MeCN)Cu2{(PhO)2P(2-py)}3](PF6)2∙3THF
We thank the Fonds der Chemischen Industrie and the
Studienstiftung des deutschen Volkes (Scholarships for S. H.),
and the EU (ERC Advanced Investigator Grant for D. S. W.) and
a Marie Curie Intra European Fellowship within the seventh
European Community Framework Programme for R.G.R.) for
financial support. The authors would like to acknowledge the
use of the EPSRC UK National Service for Computational
Chemistry Software (NSCCS) at Imperial College London in
carrying out this work.
(13∙3THF). (PhO)2P(2-py) (0.103 g, 0.035 mmol) and
[Cu(MeCN)4]PF6 (0.087 g, 0.023 mmol) in MeCN (10 mL) were
brought to reflux overnight. The solvent was removed under
reduced pressure, resulting in an orange oil, which was washed
with n-hexane. Yield: 0.10g, 0.074 mmol, 64 %. A few colourless
crystals could be grown from layering a saturated THF solution
1
with diethyl ether. H NMR (CD3CN), δ = 8.73 (3H, s (br), H6),
7.95 - 7.84 (6H, m, H3,4), 7.50 (3H, s (br), H5), 7.39 - 7.30 (12H,
Ph-H), 7.24 - 7.10 (18H, Ph-H), 1.99 (MeCN solvent residual
signal partially overlaps with the signal of the coordinated
MeCN molecules). 31P{1H} NMR (CD3CN), δ = 120.7 (s, br), -144.6
(sep, JPF = 705.6, PF6). 13C{1H} NMR (CD3CN), δ = 154.04 (s, Ph-
Cq), 151.4 (d, JCP = 18.9, C6), 137.9 (s, C3/4), 130.8 (s, Ph), 127.2
(s (br),C5), 127.1 (s (br), C3/4), 126.2 (s, Ph), 121.9 (d, JCP = 5.2,
Ph), 117.3 (MeCN), 1.32 (MeCN). Correct elemental analysis
could not be obtained due to the presence of free PhOH as a
contaminant.
Notes and references
§
Primary amino substituents (RNH) were not employed
because the reactions of primary amines (RNH2) with PCl3
normally produce P-N ring compounds.84
§§
Since the bulk purity of 1 could be improved, (Me2N)2PCl,
instead of the more easily assessable ethyl congener (Et2N)2PCl
was selected as precursor.
Synthesis of [{OP(O)(H)(2-py)}Cu2{(PhO)2P(2-py)}2]2(PF6)2
§§§ It is not possible to synthesise ClxP(2-py)3-x by variation of
the stoichiometry in the reaction of PCl3 with Li(2-py) because
∙2THF (14∙2THF). The reaction of 0.12 g of (PhO)2P(2-py) (9)
(0.41 mmol) and [Cu(MeCN)4]PF6 (0.103 g, 0.28 mmol) in 12 mL
8 | J. Name., 2012, 00, 1-3
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only the tri-substituted compound P(2-py)3 is obtained.12 Only
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of (RO)xPCl3-x and Li(2-py) only resulted in the formation of an
intractable mixture of products.
25
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The incorporation of a
Multidentate 2-pyridyl-
variety of alcohols into
phosphine ligands – towards
ligand tuning and chirality
(amino)pyridyl-phosphine
frameworks provides access
to a library of multidentate
(alkoxy)pyridyl-phosphines.
Their coordination chemistry
with CuI is explored.
S. Hanf, R. García-Rodríguez, S.
Feldmann, A. D. Bond, E. Hey-
Hawkins and D. S. Wright