Synthesis of alkenyl ylide complexes from reactions of ReOCl 2(OEt)(PPh3)2 with alkynols

Article abstract of DOI:10.1021/om3005788

Reactions of both terminal and internal alkynols with ReOCl ₂(OEt)(PPh₃)₂ (1) are described. Treatment of ReOCl₂(OEt)(PPh₃)₂ (1) with HC≡CC ₆H₄-2-CH₂OH and HC≡CCH₂CH ₂CH₂OH produced the six-membered ylide complexes ReOCl₂(C(=CH(PPh₃))-C₆H₄-CH ₂O)(PPh₃) (2) and ReOCl₂(C(=CH(PPh ₃))CH₂CH₂CH₂O)(PPh₃) (3), respectvely, derived from addition of PPh₃ to the terminal alkyne carbon. Similarly, phosphine addition to the terminal alkyne carbon occurred in the reactions of ReOCl₂(OEt)(PPh₃)₂ (1) with HC≡CCH₂CH(OH)Me and HC≡CCH₂CH(OH)CH(OH)CH ₂C≡CH to give the five-membered ylide complexes ReOCl ₂(C(=CH(PPh₃))CH₂CH₂CHMeO)(PPh ₃) (5) and {ReOCl₂(C(=CH(PPh₃)CH ₂CHO)(PPh₃)}₂ (6), respectively. Interestingly, related reactions of ReOCl₂(OEt)(PPh₃)₂ with RC≡CCH₂CH₂OH (R = Me, Et, Ph) produced the six-membered ylide complexes ReOCl₂(CR=C(PPh₃)CH ₂CH₂O)(PPh₃) (7, R = Me; 8, R = Et; 9, R = Ph), derived from addition of PPh₃ to the alkyne carbon closer to the OH group.

Full text of DOI:10.1021/om3005788

Article
pubs.acs.org/Organometallics
Synthesis of Alkenyl Ylide Complexes from Reactions of
ReOCl (OEt)(PPh ) with Alkynols
2
3 2
Ka Chun Poon, Chuan Shi, Herman H.-Y. Sung, Ian D. Williams, Zhenyang Lin,* and Guochen Jia*
Department of Chemistry, Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, People's
Republic of China
*
S Supporting Information
ABSTRACT: Reactions of both terminal and internal
alkynols with ReOCl (OEt)(PPh ) (1) are described. Treat-
2
3 2
ment of ReOCl (OEt)(PPh ) (1) with HCCC H -2-
2
3 2
6
4
CH OH and HCCCH CH CH OH produced the six-
2
2
2
2
membered ylide complexes ReOCl (C(CH(PPh ))-C H -
2
3
6
4
CH O)(PPh ) (2) and ReOCl (C(CH(PPh ))CH CH CH O)(PPh ) (3), respectvely, derived from addition of PPh to the
2
3
2
3
2
2
2
3
3
terminal alkyne carbon. Similarly, phosphine addition to the terminal alkyne carbon occurred in the reactions of
ReOCl (OEt)(PPh ) (1) with HCCCH CH(OH)Me and HCCCH CH(OH)CH(OH)CH CCH to give the five-
2
3 2
2
2
2
membered ylide complexes ReOCl (C(CH(PPh ))CH CH CHMeO)(PPh ) (5) and {ReOCl (C(CH(PPh )CH CHO)-
2
3
2
2
3
2
3
2
(
PPh )} (6), respectively. Interestingly, related reactions of ReOCl (OEt)(PPh ) with RCCCH CH OH (R = Me, Et, Ph)
3
2
2
3 2
2
2
produced the six-membered ylide complexes ReOCl (CRC(PPh )CH CH O)(PPh ) (7, R = Me; 8, R = Et; 9, R = Ph),
2 3 2 2 3
derived from addition of PPh to the alkyne carbon closer to the OH group.
3
INTRODUCTION
ported to react with PMe3 to give a mixture of [ReO-
■
Me (PhCCHPMe )(bipy)]PF and [ReOMe (HC
2
3
6
2
Nucleophilc additions of phosphines to coordinated alkynes or
2
2
CPhPMe )(bipy)]PF . ReOX (PPh ) (X = Cl, Br) were
3
6
3
3 2
formal insertion of alkynes into M−PR bonds provide a
3
reported to react with phenylacetylene to give a mixture of
species, from which complexes such as ReOCl (PPh ){C(Ph)-
convenient route to metal alkenyl ylide complexes. Reactions of
such type have been demonstrated with complexes containing
3
3
1
2
3
4,5
6−8
9
10
CH(PPh )}, ReOBr (OPPh ){C(Ph)CH(PPh )}, and
3 3 3 3
metals such as Pd, Co, Rh, Ir, Ru,
Mn, and Mo.
ReOBr (OPPh ){CHC(Ph)(PPh )} could be isolated in low
3
3
3
Recently the chemistry has been applied to the synthesis of
24
1
1,12
15
yields (3−5%) (Scheme 1). To the best of our knowledge,
additions of phosphines to coordinated internal alkynes have
not been reported for rhenium systems.
interesting metallacycles, for example, ruthenabenzenes,
1
3
14
osmabenzenes, ring-fused osmabenzenoids, osmafurans,
16
17
isoosmabenzenes, and iridacyclohexadienes, from reactions
of phosphine-containing complexes with appropriate alkynes.
During our effort to develop the chemistry of rhenaben-
For practical applications, it is still necessary to find systems
and strategies that can give alkenyl ylide complexes in high
yields from the reactions of both internal and terminal alkynes.
1
8
19
zenes and rhenabenzynes, we become interested in
nucleophilic additions of phosphine to coordinated alkynes in
rhenium systems in view of the possibility of preparing new
rhenabenzenes or rhenabenzynes with the chemistry. A survey
of the literature suggests that limited work has been previously
carried out for addition reactions of phosphines to coordinated
alkynes in rhenium systems. The addition reactions of
phosphines to the CC bonds of the simplest alkyne HC
CH coordinated to rhenium were observed in the reactions of
Scheme 1
20
HCCH with Re(O)R (PMe ) (R = Me, CH SiMe ), cis-
3
3
2
3
2
0
Re(O)Me Cl(PMe R) (R = Me, Ph),
and Re-
2
2
2
21
(
[
NAr) (PMe Ph)(CH CMe ) and in the reactions of trans-
2 2 2 3
2
2
ReOMe (HCCH)(bipy)]PF
and [Re Cl (μ-
2 3
2
6
2
3
dppm) (CO)(HCCH)]X (X = PF , O SCF ) with
2
6
3
3
phosphines such as PMe and PPh Related transformations
3
3.
involving terminal alkynes RCCH are limited to the
following few examples. [Re Cl (μ-dppm) (CO)(RC
2
3
2
CH)]X (X = PF , O SCF ; R = Ph, n-Pr, n-Bu) were reported
6
3
3
to react with PR′ to give [Re Cl (μ-dppm) (CO)(RC
Received: June 23, 2012
Published: October 2, 2012
3
2
3
2
2
3
CHPR′ )]X. trans-[ReOMe (PhCCH)(bipy)]PF was re-
3
2
6
©
2012 American Chemical Society
7085
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Organometallics
Article
The reactions of ReOX (PPh ) (X = Cl, Br) with phenyl-
Complex 2 is sparingly soluble in dichloromethane,
moderately soluble in chloroform, and slightly soluble in
acetone and THF. Its structure has been confirmed by X-ray
diffraction studies. The selected bond distances and angles of 2
are given in Table 1. The X-ray diffraction study confirms that
3
3 2
acetylene, although giving a mixture of species in low yields
3−5%), are particularly interesting to us, as it demonstrates
(
that readily available Re(V) halophosphine complexes can react
with terminal alkynes to give alkenyl ylide complexes, which
contain ligands that could be easily displaced by others for
further manipulations. For this reason, we have investigated the
reactions of alkynes with various Re(V) halophosphine
complexes, in order to find out strategies to obtain alkenyl
ylide complexes in high yields from the reactions of Re(V)
complexes with alkynes. In this work, we report the results from
the reactions of ReOCl (OEt)(PPh ) with both terminal and
Table 1. Selected Bond Lengths (Å) and Angles (deg) for 2
and 3
compd
2
3
Re(1)−P(2)
Re(1)−Cl(1)
Re(1)−Cl(2)
Re(1)−O(1)
2.4295(14)
2.4752(13)
2.4397(13)
1.897(3)
2.4621(16)
2.4405(15)
2.4974(16)
1.880(4)
2
3 2
internal alkynols.
RESULTS AND DISCUSSION
Re(1)−O(2)
Re(1)−C(2)
C(1)−C(2)
P(1)−C(1)
1.698(3)
1.702(4)
■
2.124(4)
2.067(6)
Reaction of ReOCl (OEt)(PPh ) with Terminal Alky-
2
3 2
1.351(6)
1.387(7)
nols. As mentioned previously, complexes ReOX (PPh ) (X =
3
3 2
1.769(4)
1.774(6)
Cl, Br) were reported to react with phenylacetylene to give a
mixture of alkenyl ylide complexes in low yields (3−5%). We
reasoned that if an alkyne is first tethered to rhenium, the
reaction may be cleaner, which may allow one to isolate the
resulting alkenyl ylide complexes in good yields. It is known
that the OEt group in ReOCl (OEt)(PPh ) can be replaced by
P(2)−Re(1)−Cl(1)
P2−Re(1)−Cl(2)
Cl(1)−Re(1)−Cl(2)
O(2)−Re(1)−P(2)
O(2)−Re(1)−Cl(1)
O(2)−Re(1)−Cl(2)
O(2)−Re(1)−O(1)
O(2)−Re(1)−C(2)
O(1)−Re(1)−P(2)
O(1)−Re(1)−Cl(1)
O(1)−Re(1)−Cl(2)
O(1)−Re(1)−C(2)
C(2)−Re(1)−P(2)
C(2)−Re(1)−Cl(1)
C(2)−Re(1)−Cl(2)
174.85(4)
86.81(4)
177.73(7)
90.62(5)
88.15(4)
87.44(5)
89.92(11)
92.25 (11)
103.15(11)
172.21(14)
90.38(16)
90.80(10)
87.69 (10)
84.68(9)
84.72(13)
94.41(13)
98.70(14)
172.33(18)
90.6(2)
2
3 2
an aryloxide or alkoxide ligand upon treatment with phenols or
2
5
alcohols. We have therefore carried out the reactions of
ReOCl (OEt)(PPh ) with alkynols RCC−X−OH (X = a
2
3 2
89.32(11)
91.72(11)
86.16(13)
85.37(19)
97.57(15)
84.52(15)
168.13(16)
linking group), hoping that the reactions would proceed
through the intermediates ReOCl (O−X−CCR)(PPh )
2
3 2.
We first studied the reactions of ReOCl (OEt)(PPh ) (1)
2
3 2
81.79(15)
97.73(13)
86.93(13)
165.78(13)
with alkynols in which the OH and CC moieties are
separated by three carbons. Treatment of ReOCl (OEt)-
2
(
PPh ) (1) with 2-ethynylbenzyl alcohol at room temperature
3 2
in acetone produced the expected ylide complex 2 (Scheme 2)
Scheme 2. Reactions of 1 with Terminal Alkynols
the complex has a six-membered-ring structure possessing a
CC bond located outside of the ring. As shown in Figure 1,
complex 2 has a distorted-octahedral geometry around rhenium
with a chloride ligand trans to the carbon of the ylide ligand
as the only ylide complex, which was formed by addition of a
phosphine ligand to the terminal alkyne carbon. The formation
of 2 is visually marked by a color change of the suspension from
brown to purple. The air-stable purple complex was isolated in
high yield after recrystallization from dichloromethane and
hexane. It is noted that the reaction between ReOX (PPh ) (X
3
3 2
=
Br, Cl) and phenylacetylene gives a mixture of products
resulting from phosphine addition to both terminal and internal
acetylene carbons. Complex 2 can be also produced from the
24
reaction of the rhenium oxo hydride complex ReOCl H(PPh )
2
3 2
(
4) with 2-ethynylbenzaldehyde in dichloromethane at room
Figure 1. Molecular structure of ReOCl (C(CH(PPh ))-C H -
2
3
6
4
1
31
temperature, as indicated by in situ H and P NMR.
CH O)(PPh ) (2).
2 3
7
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Organometallics
Article
and an oxo ligand trans to the oxygen atom of the alkoxyl
group. The C(2)−C(3) bond distance in the fragment
ReCArCH(PPh ) (1.351(6) Å) is close to those reported for
3
high-oxidation-state rhenium oxo ylide complexes such as
2
0
Re(O)(CH SiMe ) (CHCH(PMe )) (1.355(13) Å) and
2
3
3
3
24
ReOBr (OPPh ){C(Ph)CH(PPh )} (1.35(2) Å). The ylide
3
3
3
P−C
bond distance (1.769(4) Å) is longer than that
ylide
26
reported for Ph PCH (1.661(8) Å) and close to those
3
2
reported for high-oxidation-state rhenium oxo ylide complexes
such as Re(O)(CH SiMe ) (CHCH(PMe )) (1.737(10) Å)
and ReOBr (OPPh ){C(Ph)C(H)(PPh )} (1.758(8) Å).
2
0
2
3 3
3
2
4
3
3
3
The Re−C(2) bond distance (2.124(4) Å) is at the high end
of those reported for typical ReCR (carbene; R = H, alkyl)
2
2
7,28
bonds (1.850−2.153 Å)
and within the range of those
reported for typical Re−CR (vinyl; R = H, alkyl) bonds
2
7,29
(
2.016−2.266 Å).
The structural data suggested that the
structure of 2 has contribution from the resonance forms 2, 2A,
and 2B, with 2 being the most important.
Figure 2. Molecular structure of ReOCl (C(CH(PPh ))-
2
3
CH CH CH O)(PPh ) (3).
2
2
2
3
1
Scheme 3. Proposed Mechanism for the Formation of 3
The solid-state structure is supported by the solution H and
3
1
P NMR data. The presence of the ylide group in 2 is reflected
1
1
by the H NMR spectrum, which shows a doublet vinyl H
2
signal at 6.82 ppm with a J
coupling constant of 30.8 Hz
H−P
and the 31P{ H} NMR spectrum, which shows a downfield
1
signal at 6.1 ppm. Due to the chiral nature of the complex, the
1
H NMR spectrum of 2 shows two signals for the OCH2
2
protons at 3.9 and 4.2 ppm with a JH−H coupling constant of
1
3.2 Hz.
Aliphatic alkynols reacted with 1 similarly. Thus, the reaction
of 1 with 4-pentyn-1-ol gave the structurally similar rhena oxo
ylide complex 3 (Scheme 2). The structure of 3 is fully
supported by the NMR data and has also been confirmed by X-
ray diffraction (Figure 2). Overall, the structural parameters of
3
associated with the ylide fragment are similar to those of 2,
except that the Re−C2 bond (2.067(6) Å) is slightly shorter
than that in 2 (2.124(4) Å) and the C(1)−C(2) bond
formation of vinylidene complexes is unlikely, because there are
no prior examples of reactions of Re(V) complexes with alkyne
(
1.387(7) Å) is slightly longer than that in 2 (1.351(6) Å).
In both complexes 2 and 3, the vinyl group has an E
to give vinylidene complexes. The fact that the PPh group on
3
geometry, with the Re atom and the PPh group being trans to
the alkenyl group is trans to Re can be regarded as strong
evidence that the alkenyl group is formed by external attack of
free phosphine on coordinated alkynes.
3
each other. The stereochemistry indicates that the PPh is
3
added to the alkyne from the side opposite to rhenium. Scheme
3
shows a plausible mechanism for the formation of the
We next studied the reactions of ReOCl (OEt)(PPh ) (1)
2
3 2
complexes, using the reaction of 1 with 4-pentyn-1-ol to give 3
as an illustration. Complex 1 can undergo a metathesis reaction
with 4-pentyn-1-ol to give complex A, which loses a PPh3
followed by coordination of the CCH moiety to rhenium to
with alkynols in which the OH and CC moieties are
separated by two carbons. Treatment of ReOCl (OEt)(PPh )
2
3 2
with racemic pent-4-yn-2-ol resulted in the formation of 5,
which exists as two inseparable isomers (5A,B) in a 1:1 molar
ratio (Scheme 4), again due to the addition of phosphine to the
terminal alkyne carbon. Formation of the two isomers from the
reaction is not surprising, due to the presence of a chiral carbon
center in the alkyne pent-4-yn-2-ol. Complexes 5A,B are a pair
of diastereomers. Therefore, they have different NMR chemical
give intermediate B. Nucleophilic attack of PPh at the terminal
3
alkyne carbon in B would lead to the formation of complex 3.
Similar mechanisms have been suggested previously, for
example, for the reactions of ReOX (PPh ) (X = Cl, Br)
3
3 2
24
with phenylacetylene and for the reactions of HCCH with
2
0
rhenium complexes Re(O)R (PMe ) (R = Me, CH SiMe )
shifts. Supporting evidence for the existence of the two isomers
3
3
2
3
20
1
and cis-Re(O)Me Cl(PMe R) (R = Me, Ph). It is noted that
additions of phosphines to vinylidene and allenylidene
ligands of rhenium complexes are also known. These vinylidene
and allenylidene complexes are formed by reactions of Re(I)
complexes with terminal alkynes or alkynols. In our case,
is that the H NMR spectrum (in CDCl ) shows two sets of
2
2
2
3
30
31
characteristic signals of CH (0.47, 0.49 ppm), CH(OH) (3.50,
3
3
1
1
4.00 ppm), and CH(PPh ) (5.70 and 5.95 ppm). The P{ H}
3
NMR spectrum (in CDCl ) shows two RePPh signals at −3.9
3
3
and −0.2 ppm and two CPPh signals at −1.8 and −2.3 ppm.
3
7
087
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Organometallics
Article
Scheme 4. Reaction of 1 with Terminal 3-Alkynols
The molecular structure of one of the isomers has been
confirmed by X-ray diffraction. Selected bond distances and
angles are given in Table 2. As shown in Figure 3, the complex
Table 2. Selected Bond Lengths (Å) and Angles (deg) for 5
and 6
5
6
Figure 3. Molecular structure of ReOCl ((CCH(PPh ))CH C-
2
3
2
(
CH )O)(PPh ) (5).
3 3
Re(1)−P(2)
Re(1)−Cl(1)
Re(1)−Cl(2)
Re(1)−O(1)
Re(1)−O(2)
Re(1)−C(2)
C(1)−C(2)
P(1)−C(1)
P(2)−Re(1)−Cl(2)
P(2)−Re(1)−Cl(1)
Cl(1)−Re(1)−Cl(2)
O(2)−Re(1)−P(2)
O(2)−Re(1)−Cl(2)
O(2)−Re(1)−Cl(1)
O(2)−Re(1)−O(1)
O(2)−Re(1)−C(2)
O(1)−Re(1)−P(2)
O(1)−Re(1)−Cl(2)
O(1)−Re(1)−Cl(1)
O(1)−Re(1)−C(2)
C(2)−Re(1)−P(2)
C(2)−Re(1)−Cl(2)
C(2)−Re(1)−Cl(1)
2.4537(17)
2.4499(15)
2.4426(19)
1.924(4)
1.692(4)
2.102(6)
1.308(9)
1.769(6)
177.11(6)
88.87(5)
88.43(6)
86.98(15)
94.69(15)
104.63(15)
167.9(2)
90.5(2)
Re(1)−P(2)
Re(1)−Cl(2)
Re(1)−Cl(1)
Re(1)−O(1)
Re(1)−O(2)
Re(1)−C(2)
C(1)−C(2)
P(1)−C(1)
P(2)−Re(1)−Cl(1)
P(2)−Re(1)−Cl(2)
Cl(1)−Re(1)−Cl(2)
O(2)−Re(1)−P(2)
O(2)−Re(1)−Cl(1)
O(2)−Re(1)−Cl(2)
O(2)−Re(1)−O(1)
O(2)−Re(1)−C(2)
O(1)−Re(1)−P(2)
O(1)−Re(1)−Cl(1)
O(1)−Re(1)−Cl(2)
O(1)−Re(1)−C(2)
C(2)−Re(1)−P(2)
C(2)−Re(1)−Cl(2)
C(2)−Re(1)−Cl(1)
2.466(2)
2.440(2)
2.420(2)
1.924(4)
1.697(4)
2.075(7)
1.355(9)
1.764(7)
177.69(7)
90.29(7)
87.54(8)
84.89(18)
95.03(18)
106.48(17)
165.4(2)
90.7(3)
coordination sphere of each metal center being similar to that
of 5.
We also tried reactions involving shorter (for example, HC
CCH OH) or longer (for example, HCC(CH ) OH)
2
2 4
alkynols. Unfortunately, we have failed to isolate or identify
the expected ylide complexes from these reaction mixtures.
Reactions of ReOCl (OEt)(PPh ) with Internal Alky-
2
3 2
nols. We also examined the reactions of 1 with internal
alkynols. Treatment of ReOCl (OEt)(PPh ) with 3-pentyn-1-
2
3 2
ol at room temperature in acetone gave rise to a pink-purple
suspension. Recrystallization from dichloromethane/hexane led
to the isolation of red-purple crystals of 7 (Scheme 5). Other
internal alkynols such as 3-hexyn-1-ol and 4-phenylbut-3-yn-1-
ol reacted in a similar fashion to give the corresponding lilac
complexes 8 and 9, respectively (Scheme 5). These complexes
can be thought of as being formed by addition of phosphine to
the alkyne carbon closer to the OH group. The regiochemistry
is different from that observed in the reaction of 1 with the
90.08(15)
88.75(13)
87.07(14)
78.1(2)
87.49(15)
93.13(15)
85.98(15)
78.0(2)
related terminal alkynol 4-pentyn-1-ol, where PPh adds to the
3
95.65(17)
86.69(18)
164.43(18)
97.7(2)
alkyne carbon farther away from the OH group to give the five-
membered ylide complex 5.
84.6(2)
161.72(19)
The structure of complex 8 (Figure 5) has been confirmed by
X-ray diffraction. As shown in Figure 5, complex 8 possesses a
six-membered-ring system having both carbon atoms of the
CC functional group as parts of the ring. The Re−C and
CC bond distances associated with the Re−C(Et)C
fragment are similar to those of 3. The solid-state structure is
has a five-membered-ring structure possessing a CC bond
located outside of the ring. The coordination sphere of 5 is
similar to those of 2 and 3. The C(1)−C(2) bond distance of 5
(
(
1.308(9) Å) is shorter than those of 2 (1.351(6) Å) and 3
1.387(7) Å). The ylide P−C bond distance (1.769(6) Å) is
fully consistent with the solution NMR data. For example, the
ylide
1
similar to those of 2 and 3. The Re−C(2) bond distance
H NMR spectrum of 8 shows the CH signal at 0.17 ppm and
3
31
1
(
(
2.102(6) Å) is between those of 2 (2.124(4) Å) and 3
2.067(6) Å).
the OCH signals at 2.80 and 3.63 ppm. The P{ H} NMR
2
spectrum shows two signals at −1.7 and 6.3 ppm.
DFT Studies on the Relative Stabilities of Five- and
Six-Membered Metallacycles. It is interesting to note that
Reaction of 1 with the diynol octa-1,7-diyne-4,5-diol led to
the isolation of the dinuclear rhenium oxo ylide complex 6,
which has very low solubility in common organic solvents, even
in hot dichloromethane. Fortunately, crystals suitable for X-ray
analysis could be obtained from hot dichloromethane and its
structure has been confirmed by X-ray diffraction. As shown in
Figure 4, complex 6 is a dinuclear complex, with the
terminal alkynols HCCCH CHROH (HC
2
CCH CHMeOH and HCCCH CH(OH)CH(OH)-
2
2
CH CCH) and internal alkynols RCCCH CH OH (R =
2
2
2
Me, Et, Ph) react with ReOCl (OEt)(PPh ) (1) with different
2
3 2
regiochemistries. In the reactions involving HC
7
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Organometallics
Article
Figure 4. Molecular structure of {ReOCl (C(CH(PPh ))CH CHO)(PPh )} (6).
2
3
2
3
2
Scheme 5. Reaction of 1 with Internal Alkynols
CCH CHROH, a phosphine ligand adds to the terminal carbon
2
or the alkyne carbon remote from the OH group to give five-
membered metallacycles. In the reactions involving internal
alkynols RCCCH CH OH, a phosphine ligand adds to the
2
2
alkyne carbon closer to the OH group to give six-membered
metallacycles. To have a better understanding of the different
regiochemistries, we have computed the relative energies of
complexes 7 and 10−12. Complexes 10 and 11 are the
products (or assumed products) formed from the reaction of
the rhenium oxo complex ReOCl (OEt)(PPh ) with HC
Figure 5. Molecular structure of ReOCl (CEtC(PPh )CH CH O)-
2
3
2
2
(
PPh ) (8). Selected bond distances (Å) and angles (deg): Re(1)−
3
P(2) = 2.4507(13), Re(1)−Cl(1) = 2.4923(12),Re(1)−Cl(2) =
.4445(13), Re(1)−O(1) = 1.894(3), Re(1)−O(2) = 1.704(4),
Re(1)−C(1) = 2.121(5), C(1)−C(2) = 1.377(7), P(1)−C(2) =
.799(5); P(2)−Re(1)−Cl(2) = 174.37(4), P(2)−Re(1)−Cl(1) =
88.84(4), Cl(1)−Re(1)−Cl(2) = 87.34(5), O(2)−Re(1)−P(2) =
8.56(13), O(2)−Re(1)−Cl(2) = 95.95(13), O(2)−Re(1)−Cl(1) =
2
2
3 2
CCH CH OH, having a PPh adding to the terminal (HC)
2
2
3
1
and internal (CCH ) alkyne carbons, respectively. Com-
2
plexes 12 and 7 are the products (or assumed products) formed
8
from the reaction of the rhenium oxo complex ReOCl (OEt)-
96.03(12) O(2)−Re(1)−O(1) = 176.40(15), O(2)−Re(1)−C(1 =
91.33(18), O(1)−Re(1)−P(2) = 89.01(11), O(1)−Re(1)−Cl(2) =
86.64(11), O(1)−Re(1)−Cl(1) = 86.57(11), O(1)−Re(1)−C(1) =
2
(
PPh ) with MeCCCH CH OH, having a PPh adding to
3
2
2
2
3
the MeC and CCH carbons, respectively. The results of
2
8
8
6.43(17), C(1)−Re(1)−P(2) = 98.86(13), C(1)−Re(1)−Cl(2) =
4.44(13), C(1)−Re(1)−Cl(1) = 169.49(13).
the DFT calculations are summarized in Figure 6.
The computational results indicate that, for the reaction
involving the terminal alkynol HCCCH CH OH, the five-
2
2
membered product 10 is thermodynamically more stable than
the six-membered product 11 by 2.73 kcal/mol. The reverse
was observed for the reaction involving internal alkynol MeC
CCH CH OH; the six-membered product 7 is thermodynami-
kcal/mol. The computational results are consistent with the
experimental observations that the reaction of HC
CCH CHMeOH gives five-membered metallacycle 5 while
2
that of MeCCCH CHOH gives six-membered metallacycle
2
2
2
cally more stable than the five-membered product 12 by 0.47
7.
7
089
dx.doi.org/10.1021/om3005788 | Organometallics 2012, 31, 7085−7092

Organometallics
Article
that the observed products are formed under both thermody-
namic and control.
SUMMARY
■
We have demonstrated that rhenium oxo ylide complexes can
be obtained in high yield from the reactions of both internal
and terminal alkynols with ReOCl (OEt)(PPh ) through
2
3 2
phosphine addition to one of the alkyne carbons. In the
reactions of terminal alkynols, addition of phosphine to the
terminal carbon or the alkyne carbon remote from the OH
group is observed. In the reactions involving internal alkynols
RCCCH CH OH, phosphine addition to the alkyne carbon
2
2
closer to the OH group is observed instead. The different
regioselectivities in the reactions of ReOCl (OEt)(PPh ) with
2
3 2
terminal alkynols HCCCH CHROH and internal alkynols
2
RCCCH CH OH can be explained in terms of the effect of
2
2
chelating ring sizes and steric interactions.
Figure 6. Relative energies of five- and six-membered metallacycles.
The relative Gibbs free energies and electronic energies (in
parentheses) at 298 K are given in kcal/mol.
EXPERIMENTAL SECTION
■
All manipulations were carried out under a nitrogen atmosphere using
standard Schlenk techniques unless otherwise stated. Solvents were
distilled under nitrogen from sodium benzophenone (hexane,
benzene, THF). The starting materials ReOCl (PPh ) , ReOHCl-
The relative stabilities of complexes 7 and 10−12 shown in
Figure 6 can be related to the structural features of the
metallacyclic complexes. It is well documented that five-
membered chelating rings lead to more stable complexes than
3
3 2
(
PPh ) , and ReOCl (OEt)PPh ) were prepared following the
3 2 2 3 2
35
procedure described in the literature. All other reagents were used
as purchased from Aldrich Chemical Co. or Strem Chemical Co.
Microanalyses were performed by M-H-W Laboratories (Phoenix,
32
six-membered chelating rings. Therefore, it is not surprising
that the five-membered metallacycle 10 is more stable than the
six-membered metallacycle 11. The reverse relative stability was
observed for the five-membered metallacycle 12 and the six-
membered metallacycle 7 (more stable). The instability of 12 in
this case can be related to the presence of a short H···O(oxo)
contact of 1.993 Å in complex 12. The H···O distance of 1.993
Å is significantly shorter than the sum (2.72 Å) of van der
1
13
1
31
1
AZ). H, C{ H}, and P{ H} spectra were collected on a Bruker
1
13
ARX-400 spectrometer (400 MHz). H and C NMR shifts are
relative to TMS, and 31P chemical shifts are relative to 85% H PO .
3
4
Preparation of 4-Phenylbut-3-yn-1-ol. In a 50 mL Schlenk flask
charged with PdCl (PPh ) (379 mg, 0.54 mmol, 5 mol %) and CuI
2
3 2
(
205 mg, 1.08 mmol, 10%) was added 20 mL of degassed
triethylamine. To this suspension was added first iodobenzene (1.1
mL, 9.8 mmol), and the mixture was stirred for 1 min before addition
of but-3-yn-1-ol (0.816 mL, 10.8 mmol). The reaction mixture turned
brown immediately and was stirred overnight. The volatiles of the
mixture were removed under reduced pressure and the residue was
extracted with diethyl ether. The ether layer collected was washed with
an ammonium chloride solution (2 × 30 mL), water (30 mL), and
finally brine (2 × 30 mL). The organic layer was collected, and the
solvent was removed under reduced pressure to give a dark brown oil,
which was subjected to flash column chromatography using 7/1
33
Waals radii of hydrogen (1.20 Å) and oxygen (1.52) atoms,
suggesting the presence of a strongly repulsive steric interaction
in complex 12. In contrast, the H···O(oxo) contacts are longer
than 2.35 Å in the six-membered metallacycle 7 (and complexes
10 and 11). Thus, the six-membered metallacycle 7 becomes
more stable than the six-membered metallacycle 12 for steric
reasons. For comparison, it is noted that the eclipsed conformer
of ethane has a H···H contact of 2.36 Å and that the staggered
conformer of ethane has a H···H contact of 2.54 Å. The
eclipsed conformer of ethane is less stable than the staggered
hexane/Et O as the eluent to give the title compound as a light brown
2
1
13
31
oil. The H and C NMR data are consistent with literature values.
34
conformer by 2.9 kcal/mol.
General Procedures for Synthesizing Rhenium Oxo Ylide
Complexes. The procedure described below was used for preparing
rhenium oxo ylide complexes unless otherwise specified. In a degassed
test tube charged with a brown suspension of ReOCl (OEt)(PPh ) in
On the basis of the above analysis, the experimentally
observed regioselectivity in the reactions of ReOCl (OEt)-
2
(
PPh3)2 with terminal alkynols HCCCH CHROH and
2
3 2
2
acetone was added 2 equiv of an alkynol. The mixture was heated to
0 °C for 12 h without stirring to give a purple, dark brown, or green
internal alkynols RCCCH CH OH can be accounted for as
2
2
6
follows. The reactions of ReOCl (OEt)(PPh ) with terminal
2
3 2
solution with lilac crystalline solids deposited on the tube’s wall. The
reaction mixture was cooled to room temperature and filtered. The
solid collected was washed with cold acetone and dried in vacuo.
Further purification can be archived by recrystallization from
dichloromethane/hexane or hot acetone.
HCCCH CHROH give five-membered metallacycles (addi-
2
tion of PPh to the alkyne carbon remote from the OH group)
3
because a five-membered chelating ring is normally thermody-
namically favored over a six-membered chelating ring. In the
reactions of ReOCl (OEt)(PPh ) with the internal alkynols
Complex 2. ReOCl (OEt)(PPh ) (250 mg, 0.297 mmol), 2-
2
3 2
2
3 2
RCCCH CH OH, five-membered metallacycles (addition of
ethynylbenzyl alcohol (79 mg, 0.594 mmol), acetone (4 mL); yield
2
2
1
2
64 mg (96%); H NMR (400.1 MHz, CDCl ) δ 3.94 (dd, J(HH) =
PPh to the alkyne carbon remote from the OH group) become
3
3
1
3.2 Hz, J(PH) = 4 Hz, 1H, OCH ), 4.20 (d, J(HH) = 13.2 Hz, 1H,
2
less favored, because the resulting five-membered metallacycle
has a significant repulsive interaction between the hydrogen of
the R group and the oxo atom. Therefore, the reactions give the
thermodynamically favored six-membered metallacycles (addi-
OCH ), 5.89 (d, J(HH) = 7.6 Hz, 1H, Ph), 6.25 (m, 2H, Ph), 6.64 (d,
2
J(HH) = 7.6 Hz, 1H,Ph), 6.82 (d, J(PH) = 30.8 Hz, 1H, CH(PPh )),
3
13
1
7
6
.1−7.9 (m, 30H, P(C H ) ); C{ H} NMR (100.6 MHz, CD Cl ) δ
6
5
3
2
2
9.8 (s, OCH ), 107.0 (d, J(PC) = 71.3 Hz, CH(PPh )), 125.0−143
2
3
tion of PPh to the alkyne carbon remote from the OH group).
31
1
3
(m, C H , P(C H ) ), 206 (d, J(PC) = 11.6 Hz, ReC); P{ H} NMR
6 4 6 5 3
The above explanation assumes that the reactions are under
thermodynamic control. We could not exclude the possibility
(162.0 MHz, CDCl ) δ 0.2 (s, CPPh ), 6.1 (s, Re-PPh ). Anal. Calcd
3 3 3
for C H Cl O P Re: C, 58.19; H, 4.02. Found: C, 58.00; H, 4.15.
45
37
2
2 2
7
090
dx.doi.org/10.1021/om3005788 | Organometallics 2012, 31, 7085−7092

Organometallics
Article
Complex 3. In a degassed test tube charged with a brown
Crystal Structure Analysis. Crystals of 2, 3, and 5 suitable for X-
ray diffraction were grown from CH Cl solutions layered with hexane,
suspension of ReOCl (OEt)(PPh ) (250 mg, 0.297 mmol) in 4 mL
2
3
2
2
2
of acetone was added 4-pentyn-1-ol (55.3 μL, 0.594 mmol). The
mixture was stirred for 6 h at 60 °C to give a dark brown solution. The
reaction mixture was cooled to room temperature, and the solvent was
dried under reduced pressure to give a dark brown oily residue, which
was redissolved in a minimal amount of CH Cl (ca. 1 mL) and
and those of 6 and 8 were grown from hot CH Cl and acetone,
2 2
respectively. All the crystals were mounted on glass fibers. The
diffraction intensity data of 2, 3, and 5 were collected with a Bruker
APEX CCD diffractometer using Mo Kα radiation (λ = 0.710 73 Å) at
100 K. Lattice determination and data collection were carried out
using SMART v.5.625 software. Data reduction and absorption
correction were performed using SAINT v 6.26 and SADABS v 2.03,
respectively. The diffraction intensity data of 6 and 8 were collected
with an Oxford Diffraction GeminiS Ultra with CCD area-detector
using Cu Kα radiation (λ = 1.5418 Å) at 173 K. Lattice determination,
data collection, and reduction were carried out using CrysAlisPro
2
2
precipitated with hexane (ca. 2 mL) to give a brown oily residue and a
purple solution. The purple solution was collected. The precipitation
procedure was repeated until the solution become yellow-brown. The
purple solutions were combined and concentrated under reduced
pressure to give a lilac precipitate, which was collected by filtration and
washed with diethyl ether (ca. 2 mL) and dried under vacuum. Yield:
38 mg (53%). 1H NMR (400.1 MHz, CD Cl ): δ 0.9 (m, 1H,
1
.171.34.40. Structure solution and refinement for all compounds were
1
2 2
performed using the Olex2 software package (which embedded
SHELXTL). All structures were solved by direct methods, expanded
by difference Fourier syntheses, and refined by full-matrix least squares
OCH CH ), 1.3 (m, 1H, OCH CH ), 2.21 (m, 1H, ReCCH ), 2.38
2
2
2
2
2
(
m, ReCCH ), 2.81 (m, 1H, OCH ), 3.35 (m, 1H, OCH ), 5.77 (d,
2 2 2
J(PH) = 35.2 Hz, 1H, CH(PPh )), 7.43−7.9 (m, 30H, P(C H ) );
3
6
5 3
2
3
1
1
on F . All non-hydrogen atoms were refined anisotropically with a
P{ H} NMR (162.0 MHz, CD Cl ) δ −2.9 (s, Re-PPh ), 0.0 (s,
CPPh ). Anal. Calcd for C H Cl O P Re·H O: C, 58.19; H, 4.02.
2
2
3
riding model for the hydrogen atoms, except as noted separately.
Further details on crystal data, data collection, and refinements are
summarized in Table S1 in the Supporting Information.
3
41 37
2
2
2
2
Found: C, 54.31, H, 4.30.
Complex 5: ReOCl (OEt)(PPh ) (250 mg, 0.297 mmol), HC
2
3
2
36
Computational Details. The Becke3LYP (B3LYP) level of
CCH CH(CH )OH (56 μL, 0.59 mmol), acetone (4 mL); yield 169
2
3
1
density functional theory was used to optimize all of the structures
studied in this work. Frequency calculations at the same level of theory
have also been performed to identify all stationary points as minima
mg (94%); H NMR (400.1 MHz, CDCl ) δ 0.47 (d, J = 6 Hz, 3H,
3
CH ), 0.49 (d, J = 6.5 Hz, 3H, CH ), 1.43 (m, 1H, CH ), 2.28 (m, 1H,
3
3
2
CH ), 2.8 (d, J = 13.2 Hz, 1H, CH ), 2.68 (m, 1H, CH ), 3.50 (m,
2
2
2
(
zero imaginary frequency). The LAN2DZ effective core potentials
OCH), 4.00 (m, OCH), 5.70 (d, J(PH) = 33.2 Hz, CH(PPh )), 5.95
37
3
and basis sets were used to describe Re. The standard 6-31G basis
(
d, J(PH) = 34 Hz, CH(PPh )), 7.4−7.8 (m, 30H, P(C H ) );
3
6
5 3
set was used for all other atoms. Polarization functions were added for
3
1
1
P{ H} NMR (162.0 MHz, CDCl ) δ −3.9 (s, Re-PPh ), −2.3 (s,
38
3
3
P (ζ(d) = 0.387), Cl (ζ(d) 0.640), and Re (ζ(f) = 0.869). 3A9 ll of the
CPPh ), −1.8 (s, CPPh ), −0.2 (s, Re-PPh ). Anal. Calcd for
C H Cl O P Re·H O: C, 54.79; H, 4.37. Found: C, 54.90; H, 4.37.
3
3
3
calculations were performed with the Gaussian 03 package.
41
37
2
2
2
2
Complex 6: ReOCl (OEt)(PPh ) (250 mg, 0.297 mmol), HC
2
3 2
ASSOCIATED CONTENT
Supporting Information
CCH CH(OH)CH(OH)CCH (20.5 mg, 0.149 mmol), acetone (4
■
2
1
*
S
mL); yield 77 mg (30%); H NMR (400.1 MHz, CD Cl ) δ 2.25 (m,
2
2
2
3
H, CH ), 2.42 (m, 2H, CH ), 2.77 (m, 2H, OCH), 5.48 (d, J(PH) =
Tables giving Cartesian coordinates and electronic energies for
all the calculated structures, a table giving crystallographic
details for complexes 2, 3, 5, 6, and 8, and CIF files giving X-ray
crystallographic data for complexes 2, 3, 5, 6, and 8. This
material is available free of charge via the Internet at http://
pubs.acs.org.
2
2
31
1
2.8 Hz, 2H, CH(PPh )), 7.2−7.8 (m, 60H, P(C H ) ); P{ H}
3
6
5 3
NMR (162.0 MHz, CD Cl ) δ −4.9 (s, Re-PPh ), −2.5 (s, CPPh ).
2
2
3
3
Anal. Calcd for C H Cl O P Re ·CH Cl : C, 53.56; H, 3.88. Found:
80
68
4
4
4
2
2
2
C, 53.06; H, 4.20.
Complex 7: ReOCl (OEt)(PPh ) (250 mg, 0.297 mmol), MeC
2
3 2
CCH CH OH (55 μL, 0.594 mmol), acetone (4 mL); yield 198 mg
2
2
1
(
76%); H NMR (400.1 MHz, CD Cl ) δ 2.05 (q, J = 11.1 Hz, 3H,
2 2
AUTHOR INFORMATION
Notes
The authors declare no competing financial interest.
OCH CH ), 2.20 (m, 1H, OCH CH ), 2.55 (d, J(PH) = 2.4 Hz, 3H,
■
2
2
2
2
CH ), 2.82 (m, 1H, CH O), 3.11 (m, 1H, CH O), 7.3−7.9 (m, 30H,
3
2
2
31
1
P(C H ) ); P{ H} NMR (162 MHz, CD Cl ) −1.1 (s, Re-PPh ), 6.3
6
5
3
2
2
3
(
s, CPPh ). Anal. Calcd for C H Cl O P Re·3CH COCH : C,
3 41 37 2 2 2 3 3
5
6.92; H, 5.25. Found: C, 57.36; H, 5.07. The sample used for the
ACKNOWLEDGMENTS
This work was supported by the Hong Kong Research Grant
Council (Project No. HKUST601408, 601709, 602611).
■
elemental analysis was obtained directly from the reaction (in acetone)
mixture.
Complex 8: ReOCl (OEt)(PPh ) (250 mg, 0.297 mmol), EtC
2
3 2
CCH CH OH (65 μL, 0.59 mmol), acetone (4 mL); yield 181 mg
2
2
1
(
68%); H NMR (400.1 MHz, CD Cl ) δ 0.17 (t, J = 7.2 Hz, 3H,
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42
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CH CH O), 5.84 (d, J = 8.0 Hz, 1H, Ph), 6.28 (td, J = 7.6 Hz, J = 1.2
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2
2
1
2
13
1
6
5
3
2
2
1
6
8.9 Hz, CH ), δ 69.0 (d, J(PC) = 6.4 Hz, OCH ), 102.3 (d, J(PC) =
2
2
9.8 Hz, CH(PPh )), 120−157 (m, C H , P(C H ) ), 215 (s, ReC);
3
6
4
6
5 3
3
1
1
P{ H} NMR (162 MHz, CD Cl ) δ −4.54 (s, Re-PPh ), 10.17 (s,
2
2
3
CPPh ). Anal. Calcd for C H Cl O P Re: C, 58.80; H, 4.36. Found:
C, 58.60, H, 4.17.
3
46 39
2
2 2
7
091
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Organometallics
Article
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(
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(
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5
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(
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dx.doi.org/10.1021/om3005788 | Organometallics 2012, 31, 7085−7092