Hydrogen shift reactions of rhenium hydrido carbyne complexes

Article abstract of DOI:10.1021/om201184m

Rhenium hydrido carbyne complexes Re(≡CCH=C(CMe₃) C≡CR)HCl(PMe₂Ph)₃ (R = H, n-pentyl) undergo 1,2-hydrogen shift reactions from the metal to the carbyne carbon atom to give complexes Re(HCCHC(CMe₃)CCR)HCl(PMe₂Ph)₃, which have two isomeric forms, namely, a metallabicyclo[3.1.0]hexatriene complex, in which the chloride is cis to the metal-bonded CH, and an alkyne-carbene complex, in which the chloride is trans to the metal-bonded CH. In contrast, a similar transformation does not occur for the analogous complex Re(≡CCH=C(CMe ₃)C≡CSiMe₃)HCl(PMe₂Ph)₃, which has a SiMe₃ group on the C≡C moiety. A computational study suggests that the difference in the reactivity of the hydrido carbyne complexes is related to steric effects in the corresponding hydride-shift products. Formation of Re(HCCHC(CMe₃)CCSiMe₃)HCl(PMe ₂Ph)₃ is not favored, mainly due to the steric interactions of the SiMe₃ group with CMe₃ and one of the phosphine ligands in the resulting metallabicyclo[3.1.0]hexatriene complex, and of the SiMe₃ group with the chloride ligand in the resulting alkyne-carbene complex.

Full text of DOI:10.1021/om201184m

Article
pubs.acs.org/Organometallics
Hydrogen Shift Reactions of Rhenium Hydrido Carbyne Complexes
Jiangxi Chen, Chuan Shi, Herman Ho-Yung Sung, Ian Duncan Williams, Zhenyang Lin,*
and Guochen Jia*
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
S
* Supporting Information
ABSTRACT: Rhenium hydrido carbyne complexes Re(
CCHC(CMe3)CCR)HCl(PMe2Ph)3 (R = H, n-pentyl)
undergo 1,2-hydrogen shift reactions from the metal to the
carbyne carbon atom to give complexes Re(HCCHC(CMe3)-
CCR)HCl(PMe2Ph)3, which have two isomeric forms, namely,
a metallabicyclo[3.1.0]hexatriene complex, in which the
chloride is cis to the metal-bonded CH, and an alkyne−
carbene complex, in which the chloride is trans to the metal-
bonded CH. In contrast, a similar transformation does not occur for the analogous complex Re(CCHC(CMe3)C
CSiMe3)HCl(PMe2Ph)3, which has a SiMe3 group on the CC moiety. A computational study suggests that the difference in
the reactivity of the hydrido carbyne complexes is related to steric effects in the corresponding hydride-shift products. Formation
of Re(HCCHC(CMe3)CCSiMe3)HCl(PMe2Ph)3 is not favored, mainly due to the steric interactions of the SiMe3 group with
CMe3 and one of the phosphine ligands in the resulting metallabicyclo[3.1.0]hexatriene complex, and of the SiMe3 group with
the chloride ligand in the resulting alkyne−carbene complex.
Scheme 1
INTRODUCTION
■
1,2-Hydrogen shift from the metal to the carbyne carbon atom
in hydrido carbyne complexes LnM(H)CR to give carbene
complexes LnMCHR is one of the important chemical
properties of carbyne complexes.1 Such a transformation is now
well documented for carbyne complexes of ruthenium,2
osmium,3 and tungsten.4 It has been demonstrated that the
coligands can have a significant influence on the 1,2-hydrogen
shift reactions. For example, the barriers for the hydrogen shift
reactions of [OsH(CCHCH2)(CH3CN)2(PH3)2]2+ and
OsHCl2(CCHCH2)(PH3)2 were calculated to be 19.4 and
26.3 kcal/mol, respectively.3c
Although there has been much interest in the chemistry of
rhenium carbyne complexes,5−10and stable rhenium hydrido
carbyne complexes, such as ReH(CCH3)(η2-CH2CH2)-
(PNP) (PNP = N(SiMe2CH2PCy2)2),11 [ReH2(CCH2R)-
(mq)(PPh3)2]PF6, and ReH(CCH2R)(mq)(PPh3)2 (mq =
the anion of 2-mercaptoquinoline),12 have been isolated; a 1,2-
hydrogen shift from the metal to the carbyne carbon atom has
been rarely observed for rhenium carbyne complexes.
We have recently reported that the hydrido carbyne complex
Re(CCHC(CMe3)CCH)HCl(PMe2Ph)3 (1) can
undergo 1,2-hydrogen shift from the metal to the carbyne
carbon atom to give complex Re(HCCHC(CMe3)CCH)HCl-
(PMe2Ph)3 (2), the structure of which can be best described as
a hybrid of the resonance forms 2 (metallabicylohexatriene)
and 2A (alkyne−carbene complex) with 2 being dominant
(Scheme 1).13 In contrast, a similar transformation does not
occur for the analogous complex Re(CCHC(CMe3)C
CSiMe3)HCl(PMe2Ph)3 (3), which has a SiMe3 group on the
CC moiety even when it was heated at 60 °C for 2 days in
benzene, hexane, or THF. The results suggest that the
substituent R on the CC moiety can have a significant effect
on the 1,2-hydrogen shift reactions of hydrido carbyne
complexes of the type Re(CCHC(CMe3)CCR)HCl-
(PMe2Ph)3. To further study the substituent effect on the
hydrogen shift reaction, we have prepared Re(CCH
C(CMe3)CCnC5H11)HCl(PMe2Ph)3 (7) and found that it
can also undergo hydrogen shift reaction. A computational
study has been carried out to probe the origin in the different
reactivities of these hydrido carbyne complexes.
RESULTS AND DISCUSSION
■
The precursor complex Re(CCHC(CMe3)CCnC5H11)-
HCl(PMe2Ph)3 (7) was prepared by a procedure similar to that
Received: November 26, 2011
Published: February 9, 2012
© 2012 American Chemical Society
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used for the preparation of 3.13 Treatment of ReH5(PMe2Ph)3
(4) with HCCC(OH)(CMe3)CCnC5H11 (5) in the
presence of HCl produced Re(CCHC(CMe3)C
CnC5H11)Cl2(PMe2Ph)3 (6), which was isolated as a blue
solid. Reaction of 6 with Me3CMgCl in THF gave the hydrido
carbyne complex Re(CCHC(CMe3)CCnC5H11)HCl-
(PMe2Ph)3 (7), which was isolated as a purple solid in 83%
yield (Scheme 2).
three meridionally bound PMe2Ph ligands, two mutually cis
chloride ligands, and a carbyne ligand trans to one of the
chloride ligands. The ReC bond distance is 1.767(2) Å, and
the Re−C(1)−C(2) angle is 172.3(2)°. The structural
parameters related to the metal−carbon bond are similar to
those of reported carbyne complexes, such as ReCl2(CCH
CPh2)(PMe2Ph)3,14 [ReCl(CC6H2Me3-2,4,6)(o-
(PPh2)2C6H4)]ClO4,5a and ((Me3C)2PCH2SiMe2)2N)ReH(
CCH2CMe3).11e
Consistent with the solid-state structure, the 1H NMR
spectrum showed a characteristic ReCCH signal at 4.04 ppm.
The 13C{1H} NMR spectrum showed signals at 261.4 (Re
C), 138.4 (ReCCH), 140.4 (ReCCHC(CMe3)), 101.2
(CCnC5H11), and 79.7 (CCnC5H11) ppm. The 31P{1H}
NMR spectrum showed a doublet at −17.8 ppm and a triplet at
−26.0 ppm with a coupling constant of 12.6 Hz.
Scheme 2
The structure of 7 can be assigned on the basis of the NMR
data. In particular, the 31P{1H} NMR spectrum showed a
doublet at −17.8 ppm and a triplet at −25.6 ppm with a J(PP)
coupling of 14.1 Hz, suggesting that complex 7 has three
1
meridionally bound PMe2Ph ligands. The H NMR spectrum
showed a characteristic ReCCH signal at 4.40 ppm. The
hydride signal is overlapped with those of CH2 in the region of
1.58−1.78 ppm. For comparison, the hydride signal of 3 was
observed at 1.69 ppm. The 13C{1H} NMR spectrum of 7
showed signals at 255.7 (ReC, dt, J(PC) = 14.1 and 10.8
Hz), 139.9 (ReCCH), 135.9 (ReCCHC(CMe3)), 98.1
(CCnC5H11), and 81.3 ppm (CCnC5H11). The pattern of
the ReC signal clearly indicates that the carbyne carbon is cis
to all the three phosphorus atoms.
When complex 7 in hexane was heated at 55 °C for 12 h or a
benzene solution of 7 stood at room temperature for 7 days,
two new complexes were produced in a molar ratio of 1:0.15, as
1
The new carbyne complex 6 has been characterized by NMR,
elemental analysis, and X-ray diffraction. The molecular
structure of 6 is shown in Figure 1. The complex contains
indicated by H NMR. The ratio of the two compounds does
not change with refluxing time. The major product was
identified as complex 8 and the minor one as 9 (Scheme 2).
The structure of complex 8 has been confirmed by an X-ray
diffraction study. As shown in Figure 2, it contains an
essentially planar bicyclic metallacycle. The maximum deviation
from the least-squares plane through Re1 and C1−C5 is 0.011
Å for C2. The C1−C2, C2−C3, C3−C4, and C4−C5 bond
distances are 1.355(7), 1.454(7), 1.361(7), and 1.325(7) Å,
respectively. The Re−C5 bond length (1.991(5) Å) is within
those reported for typical ReCR2(carbene, R = H or alkyl)
bonds (1.850−2.153 Å)15,16 and shorter than those reported
for Re−C bonds of rhenium−η2-alkyne (2e donor) complexes
(2.118−2.247 Å).17 The Re−C1 bond length of 2.160(5) Å is
within the range of those reported for typical Re−CH(vinyl)
bonds (1.996−2.305 Å)15,18 and longer than those reported for
typical ReCHR(carbene) bonds.15,16
Scheme 2 shows two resonance forms contributing to the
overall structure of the metallacycle of complex 8:
metallabicyclo[3.1.0]hexatriene complex (8) and alkyne−
carbene complex (8A). In view of the fact that the Re−C5
bond is significantly shorter than the Re−C1 bond, we consider
that resonance form 8 is the dominant one. DFT calculations
further support that resonance form 8 makes a greater
contribution to the overall structure of 8. As shown in Figure
3, the optimized structure reproduces well the structural feature
of 8 described above. The calculated Wiberg bond indices
(which are a measure of bond strength) of Re−C1, Re−C4,
and Re−C5 are 0.664, 0.638, and 1.034, respectively. The data
Figure 1. ORTEP drawing of 6 with thermal ellipsoids at the 35%
probability level. The hydrogen atoms on PMe2Ph ligands and the n-
pentyl group are omitted for clarity. Selected bond lengths [Å] and
angles [deg]: Re(1)−C(1) 1.767(2), C(1)−C(2) 1.427(3); C(2)−
C(1)−Re(1) 172.3(2), C(2)−C(3)−C(4) 118.5(2).
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at 236.8 ppm (dt, J(PC) ≈ 12.4 Hz, 9.8 Hz). The magnitude of
the J(PC) couplings for the ReCH signal implies that the
CH is cis to all the phosphorus atoms. In contrast, the
corresponding ReCH signal of 8 appears at 172.1 ppm. The
coupling (39.8 Hz) between this carbon and the unique P is
significantly larger as expected. The 13C signals associated with
the CC moiety in 9 were observed at 148.5 (CCnC5H11)
and 118.1 (CCnC5H11) ppm. For comparison, the 13C signals
of η2-PhCCH in Re(Br)(H)(NO)(PCy3)2(η2-HCCPh)
were observed at 106.9 (s, CPh) and 106.8 (s, HC)
ppm16a and those of η2-PhCCPh in Re(CO)(NO)-
(PMe3)2(η2-PhCCPh) were observed at 137.6 and 144.9
ppm.19 The NMR data suggest that the structure of 9 has
contributions from the resonance forms 9 (alkyne−carbene
complex) and 9A (metallabicylohexatriene) with 9 being
dominant.
While we have not been able to get crystals of 9 suitable for
X-ray diffraction analysis, further information on the structure
of 9 comes from the DFT study, which supports the description
mentioned above. In the optimized structure of 9 (Figure 4),
the C1−C2, C2−C3, C3−C4, and C4−C5 bond distances are
1.450, 1.367, 1.423, and 1.277 Å, respectively. The Re−C5
bond length (2.184 Å) is within those reported for Re−C
bonds of rhenium−η2-alkyne (2e donor) complexes (2.118−
2.247 Å)17 and longer than those reported for typical Re
CR2(carbene, R = H, alkyl) bonds (1.850−2.153 Å).15,16 The
Re−C1 bond length (1.956 Å) is within the range of those
reported for typical ReCR2(carbene, R = H, alkyl) bonds
(1.850−2.153 Å)15,16 and shorter than those reported for
typical Re−CH(vinyl) bonds (1.996−2.305 Å).15,18 Further-
more, the calculated Wiberg bond indices of Re−C1, Re−C4,
and Re−C5 are 1.183, 0.463, and 0.495, respectively, suggesting
that Re−C1 can be considered as a double bond, while Re−C5
and Re−C4 as a single bond. The calculated structural
parameters, NBO analysis, and NMR data support that the
resonance form 9 has a greater contribution. Thus, it can be
best described as an alkyne−carbene complex.
Figure 2. ORTEP drawing of 8 with thermal ellipsoids at the 35%
probability level. The hydrogen atoms on PMe2Ph ligands and the n-
pentyl group are omitted for clarity. Selected bond lengths [Å] and
angles [deg]: Re(1)−C(1) 2.160(5), Re(1)−C(4) 2.085(4), Re(1)−
C(5) 1.991(5), C(1)−C(2) 1.355(7), C(2)−C(3) 1.454(7), C(3)−
C(4) 1.361(7), C(4)−C(5) 1.325(7), C(5)−C(6) 1.504(7); C(1)−
C(2)−C(3) 113.9(4), C(2)−C(1)−Re(1) 120.9(3), C(3)−C(4)−
Re(1) 126.9(4), C(4)−Re(1)−C(1) 69.88(18), C(4)−C(3)−C(2)
108.3(4), C(4)−C(5)−Re(1) 74.9(3), C(5)−Re(1)−C(1)
107.74(19), C(5)−Re(1)−C(4) 37.86(19), C(5)−C(4)−Re(1)
67.2(3), C(5)−C(4)−C(3) 165.9(5).
suggest that Re−C1 and Re−C4 bonds can be considered as
Re−C single bonds while Re−C5 as a ReC bond.
Consistent with the solid-state structure, the 31P{1H} NMR
of 8 in C6D6 showed a doublet at −29.9 ppm and a triplet at
−31.1 ppm with a J(PP) coupling constant of 13.3 Hz. The 1H
NMR in C6D6 showed the ReCHCH signals at 9.67
(ReCHCH) ppm and 8.95 (ReCHCH) ppm. The
13C{1H} NMR spectrum in C6D6 showed signals at δ 221.8
(C5), 172.1 (C1), 153.5 (C4), 146.6 (C2), and 133.6 (C3).
The 13C NMR data clearly indicate that C5 has carbene
character. The NMR as well as the structural data suggest that
complex 8 can be best described as a metallabicyclohexatriene
complex.
Alkyne−carbene complexes, complexes containing both
carbene and alkyne ligands, are interesting as they have been
suggested as reaction intermediates in many organometallic and
catalytic reactions, for example, benzannulation reactions of
Fischer chromium carbene complexes with alkynes to give
substituted phenols,20 alkyne polymerization,21 and enyne
metathesis22 catalyzed by carbene complexes. Well-character-
ized alkyne−carbene complexes have been previously reported
for metals, such as chromium, molybdenum, tungsten, and
ruthenium.23 Complex 9 represents a rare example of rhenium
alkyne−carbene complexes.
The structure of 9 can be assigned on the basis of the NMR
data. The 31P{1H} NMR spectrum of 9 in C6D6 showed a
doublet at −29.7 ppm and a triplet at −30.4 ppm with a J(PP)
coupling constant of 13.3 Hz, indicating that the three
phosphine ligands are meridionally bound to rhenium. The
1H NMR spectrum in C6D6 showed a ReCHCH signal at 13.92
ppm and a ReCHCH signal at 8.68 ppm, indicating that the
rhenium-bound CH group has carbene character. Consistent
with the carbene character of the rhenium-bound CH group,
the 13C{1H} NMR spectrum in C6D6 showed a signal of ReCH
It is interesting to note that complexes 1 and 7 can undergo
hydrogen shift reactions upon heating, whereas complex 3 is
Figure 3. Comparison of selected calculated and experimental (in parentheses) structural parameters (bond length in anstroms) and calculated
Wiberg bond indices of complex 8.
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Figure 4. Selected calculated structural parameters (bond length in angstroms) and Wiberg bond indices of complex 9.
Figure 5. Energy profiles calculated for the hydrogen shift reactions of 10, 13, 16, and 19. The relative electronic energies and Gibbs free energies (in
parentheses) at 298 K are given in kcal/mol.
stable under similar conditions. To understand the observa-
tions, we have performed the DFT study of the thermody-
namics for the hydrogen shift reactions of 10, 13, and 16 (the
model complexes of 1, 7, and 3, respectively). The results are
summarized in Figure 5. Clearly, the calculated results are in
agreement with the experimental results. The hydrogen shift
reactions involving 10 and 13 are thermodynamically favorable,
whereas that involving 16 is not.
from 16), the SiMe3 group is in close contact with the CMe3
group on the metallacycle with r(H···H) = 2.104 Å. The SiMe3
group is also in close contact with one of the PMe3 ligands with
r(H···H) = 2.118 Å. These H···H distances are significantly
shorter than the sum (2.40 Å) of van der Waals radii (1.20 Å)24
of two hydrogen atoms, suggesting the presence of strong
repulsive steric interaction in 17. As reflected by the structural
parameters, the repulsive steric interaction is reduced in the
analogous complexes 11 (one of the products from 10) and 14
(one of the products from 13). In the calculated structure of
11, the close H···H contacts involving CHCHC(CMe3)-
The different behaviors of 10, 13, and 16 could be
rationalized in term of steric effects. In the calculated structure
of the hypothetic product 17 (one of the assumed products
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CCH are longer than 2.30 Å; in the calculated structure of 14,
only one H···H contact (involving CHCHC(CMe3)CCEt)
with a H···H distance of less than 2.2 Å is present. Thus, due to
steric effects, the formation of 17 from 16 is less favored than
the formation of 11 and 14 from 10 and 13, respectively. 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 conformer
by 2.9 kcal/mol.25
group and the Cl ligand. In complex 18, one of the H atoms of
the SiMe3 group is in close contact with the Cl ligands with
r(Cl···H) = 2.826 Å. The Cl···H distance is shorter than the
sum (2.95 Å) of the van der Waals radii of one hydrogen atom
(1.20 Å) and one chlorine atom (1.75 Å),24 suggesting the
presence of repulsive steric interaction in 18. As expected, when
the alkyne carbons are moved 0.1 Å closer to the Re center, the
Cl···H distance is also shortened by ca. 0.1 Å, raising the energy
from 18 by 1.1 kcal/mol. The repulsive steric interaction
involving Cl···H contact in complexes 12 and 15 should be
insignificant as the Cl···H distances are longer than 2.9 Å. As a
result of the repulsive steric interaction involving Cl···H contact
in complex 18, the alkyne ligand cannot interact efficiently with
the rhenium center to form a strong Re−alkyne bond as those
in 12 and 15. Therefore, the formation of 18 from 16 is less
favored than the formation of 12 and 15 from 10 and 13,
respectively.
Examination of the structural parameters (Figure 6) of
alkyne−carbene complexes 12, 15, and 18 reveals that steric
To further support the above proposition, we have calculated
thermodynamics for the hydrogen shift reaction of the model
complex 19 with a CMe3 group attached to CC. On the basis
of the arguments above, it is expected that the hydrogen shift
reaction of 19 to give complexes 20 and 21 should be
thermodynamically not favorable. The expectation was
confirmed by the calculation results (Figure 5). The results
are consistent with the structural parameters of 20 and 21. In
the calculated structure of 20, the terminal CMe3 group is in
close contact with the CMe3 group on the metallacycle with
r(H···H) = 1.953 Å, and with one of the PMe3 ligands with
r(H···H) = 2.105 Å, indicating the presence of strong repulsive
steric interaction. In complex 21, one of the H atoms of the
CMe3 group is in close contact with the Cl ligand with
r(Cl···H) = 2.608 Å, again indicating the presence of strong
repulsive steric interaction.
SUMMARY
■
Rhenium hydrido carbyne complexes Re(CCHC(CMe3)-
CCR)HCl(PMe2Ph)3 (R = H, n-pentyl) undergo 1,2-
hydrogen shift reactions from the metal to the carbyne carbon
atom to give complexes Re(HCCHC(CMe3)CCR)HCl-
(PMe2Ph)3. In contrast, a similar transformation does not
occur for the analogous complex Re(CCHC(CMe3)C
CSiMe3)HCl(PMe2Ph)3, which has a SiMe3 group on the C
C moiety. A computational study suggests that the difference in
the reactivity of the hydrido carbyne complexes is related to
steric effects in the corresponding hydride-shift product.
EXPERIMENTAL SECTION
■
All manipulations were carried out under a nitrogen atmosphere using
standard Schlenck techniques unless otherwise stated. Solvents were
distilled under nitrogen from sodium benzophenone (hexane,
benzene, THF). The starting material ReH5(PMe2Ph)3 was prepared
following the procedure described in the literature.26 3-tert-Butyldeca-
1,4-diyn-3-ol was prepared from ethynylmagnesium bromide and 2,2-
dimethyldec-4-yn-3-one.27 All other reagents were used as purchased
from Aldrich Chemical Co. or Strem Chemical Co.
Figure 6. Short H···H and H···Cl contacts (in angstroms) in the
optimized structures of 11, 12, 14, 15, 17, 18, 20, and 21. R = Me.
interaction resulting from short H···H contacts involving CH
CHC(CMe3)CCR may not be the dominant factor determin-
ing the relative stability of these complexes. On the other hand,
it is noted that the Re−C(η2-alkyne) bond distances (2.311 and
2.205 Å) in complex 18 are appreciable longer than those in
complexes 15 (2.180 and 2.205 Å) and 12 (2.114 and 2.190 Å).
The longer Re−C(η2-alkyne) bond distances in 18 can be
related to the repulsive steric interaction between the SiMe3
Microanalyses were performed by M-H-W Laboratories (Phoenix,
1
AZ). H, 13C{1H}, and 31P{1H} spectra were collected on a Bruker
ARX-400 spectrometer (400 MHz). 1H and 13C NMR shifts are
relative to TMS and 31P chemical shifts relative to 85% H3PO4.
Re(C-CHC(CMe3)(CCnC5H11))Cl2(PMe2Ph)3 (6). To a
solution of ReH5(PMe2Ph)3 (2.251 g, 3.72 mmol) and 3-tert-
butyldeca-1,4-diyn-3-ol (910 mg, 4.41 mmol) in benzene (40 mL)
was slowly added hydrogen chloride in diethyl ether (1.0 M, 6.2 mL,
6.2 mmol). After the mixture was stirred at room temperature for 8 h,
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another portion of hydrogen chloride (1.0 M in diethyl ether, 3.0 mL,
3.0 mmol) was slowly added again, and the reaction mixture was
stirred for a further 12 h to give a green solution with a brownish
yellow precipitate. The reaction mixture was filtered through a filter
paper to remove the brownish yellow precipitate, which was identified
as the known paramagnetic complex fac-ReCl3(PMe2Ph)3. Yield: 912
mg, 34.7%. The solvent of the green filtrate was removed under
vacuum, and the residue was washed with methanol (3 mL × 3) with
the help of sonication to give a blue precipitate, which was collected by
filtration and dried under vacuum. Yield: 730 mg, 22.8%. 31P{1H}
NMR (161.98 MHz, CD2Cl2): δ −17.8 (d, J(PP) = 12.6 Hz), −26.0
NMR data for 8: 31P{1H} NMR (161.98 MHz, C6D6): δ −29.9 (d,
J(PP) = 13.4 Hz), −31.1 (t, J(PP) = 13.3 Hz). 1H NMR (400.13 MHz,
C6D6): δ 0.86 (t, J(HH) = 7.2 Hz, 3H, CH2CH2CH2CH2CH3), 1.05−
1.14 (m, 2H, CH2CH2CH2CH2CH3), 1.21−1.26 (m, 2H,
CH2CH2CH2CH2CH3), 1.36 (t, J(PH) = 4.0 Hz, 6H, PMe2Ph),
1.38−1.45 (m, 2H, CH2CH2CH2CH2CH3), 1.55 (d, J(PH) = 6.5 Hz,
6H, PMe2Ph), 1.66 (t, J(PH) = 3.8 Hz, 6H, PMe2Ph), 1.74 (s, 9H,
C(CH3)3), 2.90 (m, 2H, CH2CH2CH2CH2CH3), 7.00−7.50 (m, 15H,
Ph), 8.95 (ddt, J(HH) = 7.0 Hz, J(PH) ≈ 3.0, 2.6 Hz, 1H, Re-CH
CH), 9.67 (ddt, J(HH) = 7.0 Hz, J(PH) ≈ 3.8, 3.5 Hz, 1H, Re-CH).
13C{1H} NMR (100.62 MHz, C6D6): δ 221.8 (dt, J(PC) = 19.5, 9.4
Hz, ReC-n-C5H11), 172.1 (dt, J(PC) = 39.9 Hz, 18.0 Hz, Re-CH),
153.5 (t, J(PC) = 3.0 Hz, Re-CCC(CH3)3), 146.6 (dt, J(PC) = 4.6
Hz, 3.6 Hz, Re-CHCH), 142.0 (t, J(PC) = 17.6 Hz, Ph), 139.9 (d,
J(PC) = 26.3 Hz, Ph), 133.6 (t, J(PC) = 6.0 Hz, Re-CCC(CH3)3),
132.1 (d, J(PC) = 11.1 Hz, Ph), 129.8 (t, J(PC) = 4.2 Hz, Ph), 128.2
(s, Ph), 127.4 (s, Ph), 127.1 (d, J(PC) = 8.2 Hz, Ph), 126.9 (t, J(PC) =
4.0 Hz, Ph), 45.0 (d, J(PC) = 9.4 Hz, CH2CH2CH2CH2CH3), 39.8 (s,
C(CH3)3), 31.6 (s, CH2CH2CH2CH2CH3), 30.7 (s, C(CH3)3), 25.9
(s, CH2CH2CH2CH2CH3), 21.8 (s, CH2CH2CH2CH2CH3), 18.4 (d,
J(PC) = 22.4 Hz, PMe2Ph), 13.3 (s, CH2CH2CH2CH2CH3), 12.1 (t,
J(PC) = 17.2 Hz, PMe2Ph), 11.2 (t, J(PC) = 17.3 Hz, PMe2Ph). NMR
data for 9: 31P{1H} NMR (161.98 MHz, C6D6): δ −29.7 (d, J(PP) =
13.0 Hz), −30.4 (t, J(PP) = 13.3 Hz). 1H NMR (400.13 MHz, C6D6):
δ 1.03 (t, J(HH) = 6.8 Hz, 3H, CH2CH2CH2CH2CH3), 1.14−1.18 (m,
2H, CH2CH2CH2CH2CH3), 1.18−1.26 (m, 12H, PMe2Ph), 1.38−1.45
(m, 4H, CH2CH2CH2CH2CH3), 1.65 (s, 9H, C(CH3)3), 1.88 (d,
J(PH) = 7.2 Hz, 6H, PMe2Ph), 2.58 (t, J(HH) = 8.0 Hz, 2H,
CH2CH2CH2CH2CH3), 7.00−7.50 (m, 15H, Ph), 8.68 (d, J(HH) =
5.0 Hz, 1H, ReCH-CH), 13.92 (ddt, J(HH) = 5.1 Hz, J(PH) ≈
18.5, 3.2 Hz, 1H, ReCH). 13C{1H} NMR (100.62 MHz, C6D6): δ
236.8 (dt, J(PC) ≈ 12.4, 9.8 Hz, ReCH), 157.4 (dt, J(PC) ≈ 3.7, 2.5
Hz, Re(CH-CHCC(CH3)3)), 155.2 (dt, J(PC) ≈ 9.0 Hz, 2.6 Hz,
Re-CHCH), 148.5 (dt, J(PC) = 15.4 Hz, 7.7 Hz, CCnC5H11),
143.9 (d, J(PC) = 30.2 Hz, Ph), 141.5 (t, J(PC) = 19.1 Hz, Ph), 129.9
(t, J(PC) = 4.5 Hz, Ph), 129.7 (s, Ph), 127.3 (s, Ph), 127.2 (s, Ph),
126.7 (t, J(PC) = 3.9 Hz, Ph), 118.1 (br, CCnC5H11), 38.2 (s,
C(CH3 )3 ), 34.0 (s, CH2 CH2 CH2 CH2 CH3 ), 32.5 (s,
CH2 CH2 CH2 CH2 CH3 ), 31.5 (s, C(CH3 )3 ), 30.5 (s,
CH2CH2CH2CH2CH3), 22.0 (s, CH2CH2CH2CH2CH3), 17.0 (d,
J(PC) = 26.3 Hz, PMe2Ph), 14.4 (t, J(PC) = 14.1 Hz, PMe2Ph), 13.5
(s, CH2CH2CH2CH2CH3), 12.3 (t, J(PC) ≈ 12.1 Hz, PMe2Ph).
Crystal Structure Analysis. The crystal of 6 was grown by slowly
evaporating the solvent from its saturated solution in hexane. The
crystal of 8 was grown from a benzene solution layered with hexane at
4 °C. The diffraction intensity data of 6 and 8 were collected with an
Oxford Diffraction Gemini S Ultra X-ray diffractometer with
monochromatized Cu Kα radiation (λ = 1.54178 Å). Lattice
determination, data collection, and reduction were carried out using
CrysAlisPro 171.33.46. Absorption correction was performed using the
built-in SADABS program and the CrysAlisPro program suite.
Structure solution and refinement for all compounds were performed
using the Olex2 software28 package (which embedded SHELXTL29).
All the structures were solved by direct methods, expanded by
difference Fourier syntheses and refined by full matrix least-squares on
F2. All non-hydrogen atoms were refined anisotropically with a riding
model for the hydrogen atoms, except noted separately. Further details
on crystal data, data collection, and refinements are summarized in
Table 1.
1
(t, J(PP) = 12.5 Hz). H NMR (400.13 MHz, CD2Cl2): δ 0.90 (t,
J(HH) = 7.0 Hz, 3H, CH2CH2CH2CH2CH3), 0.98 (s, 9H, t-Bu),
1.25−1.47 (m, 4 H, CH2CH2CH2CH2CH3), 1.53 (d, J(PH) = 9.6 Hz,
6H, PMe2Ph), 1.58−1.68 (m, 2H, CH2CH2CH2CH2CH3), 1.89 (t,
J(PH) = 3.2 Hz, 6H, PMe2Ph), 2.07 (t, J(PH) = 3.4 Hz, 6H, PMe2Ph),
2.45 (t, J(HH) = 7.0 Hz, 2H, CH2CH2CH2CH2CH3), 4.04 (br s, 1H,
ReC-CHC), 6.16 (t, J(PH) = 8.7 Hz, 2H, Ph), 6.93 (t, J(HH) =
7.2 Hz, 2H, Ph), 7.10 (t, J(HH) = 7.2 Hz, 1H, Ph), 7.33−7.55 (m,
10H, Ph). 13C{1H} NMR (100.62 MHz, CD2Cl2): δ 261.4 (dt, J(PC)
= 15.4 Hz, 15.0 Hz, ReC), 141.8 (t, J(PC) = 19.6 Hz, Ph), 140.6 (d,
J(PC) = 47.5 Hz, Ph), 140.4 (q, J(PC) = 3.5 Hz, ReC-CHC),
138.4 (q, J(PC) = 3.2 Hz, ReC-CHC), 129.8 (t, J(PC) = 4.4 Hz,
Ph), 128.6 (d, J(PC) = 8.6 Hz, Ph), 128.2 (s, Ph), 127.5 (s, Ph), 127.5
(t, J(PC) = 3.8 Hz, Ph), 126.6 (d, J(PC) = 9.0 Hz, Ph), 101.2 (s, C
C-n-C5H11,), 79.7 (s, CC-n-C5H11), 35.6 (s, C(CH3)3), 30.6 (s,
CH2 CH2 CH2 CH2 CH3 ), 27.5 (s, C(CH3 )3 ), 27.2 (s,
CH2CH2CH2CH2CH3), 21.5 (s, CH2CH2CH2CH2CH3), 19.9 (s,
CH2CH2CH2CH2CH3), 18.9 (d, J(PC) = 35.2 Hz, PMe2Ph), 18.1 (t,
J(PC) = 18.0 Hz, PMe2Ph), 13.1 (s, CH2CH2CH2CH2CH3), 10.7 (t,
J(PC) = 14.7 Hz, PMe2Ph). Anal. Calcd. for C38H54Cl2P3Re: C, 53.02;
H, 6.32. Found: C, 53.09; H, 6.37.
Re(C-CHC(CMe3)CCnC5H11)HCl(PMe2Ph)3 (7). To a
solution of 6 (500 mg, 0.58 mmol) in THF (15 mL) was slowly
added tert-butylmagnesium chloride (1.0 M in THF, 2.8 mL, 2.8
mmol). After the mixture was stirred at room temperature for 40 min,
the solvent of the reaction mixture was removed under vacuum and
the residue was carefully treated with methanol (3 mL) to quench the
excess tert-butylmagnesium chloride, and then all the solvents were
removed under vacuum again. The residue was extracted with hexane
(10 mL × 3). The solvent of the filtrate was removed under vacuum to
give a purple solid, which was dried under vacuum. Yield: 397 mg,
82.7%. 31P{1H} NMR (161.98 MHz, C6D6): δ −17.8 (d, J(PP) = 14.1
1
Hz), −25.6 (t, J(PP) = 13.7 Hz). H NMR (400.13 MHz, C6D6): δ
0.95 (t, J(HH) = 7.2 Hz, 3H, CH3), 1.10 (s, 9H, C(CH3)3), 1.28−1.39
(m, 2H, CH2), 1.39−1.49 (m, 2H, CH2), 1.58 (d, J(PH) = 7.8 Hz, 6H,
PMe2Ph), 1.58−1.78 (m, 3H, ReH and CH2), 2.11 (t, J(PH) = 3.3 Hz,
6H, PMe2Ph), 2.29 (t, J(HH) = 7.1 Hz, 2H, CH2), 2.34 (t, J(PH) = 3.4
Hz, 6H, PMe2Ph), 4.40 (br, 1H, ReC-CHC), 7.00−7.26 (m, 11H,
Ph), 7.58−7.72 (m, 4H, Ph). 13C{1H} NMR (100.62 MHz, C6D6): δ
255.7 (dt, J(PC) = 10.8 Hz, 14.1 Hz, ReC), 144.4 (t, J(PC) = 16.9
Hz, Ph), 144.2 (d, J(PC) = 33.6 Hz, Ph), 139.9 (br, ReC-CHC),
135.9 (q, J(PC) = 2.8 Hz, ReC-CHC), 129.5 (t, J(PC) = 4.6 Hz,
Ph), 129.0 (d, J(PC) = 9.5 Hz, Ph), 127.4 (s, Ph), 127.2 (t, J(PC) = 3.9
Hz, Ph), 126.9 (d, J(PC) = 7.4 Hz, Ph), 126.8 (s, Ph), 98.1 (s, CC),
81.3 (s, CC), 35.5 (s, C(CH3)3), 30.7 (s, CH2), 28.0 (dt, J(PC) =
18.8 Hz, 3.0 Hz, PMe2Ph), 27.8 (s, C(CH3)3), 27.7 (s, CH2), 21.7 (s,
CH2), 19.8 (s, CH2), 16.9 (d, J(PC) = 25.3 Hz, PMe2Ph), 16.6 (t,
J(PC) =15.9 Hz, PMe2Ph), 13.3 (s, CH3). Anal. Calcd for
C38H55ClP3Re: C, 55.23; H, 6.71. Found: C, 54.98; H, 6.52.
Computational Study. The mPW1K (modified Perdew−Wang 1-
parameter for kinetics) DFT exchange-correlation functional theory of
Truhlar and co-workers30 was used to optimize all of the structures
studied in this work. This functional is based on the Perdew−Wang
exchange functional31 with Adamo and Barone’s modified enhance-
ment factor32 and the Perdew−Wang correlation functional.
Frequency calculations at the same level of theory have also been
performed to identify all stationary points as minima (zero imaginary
frequency) or transition states (one imaginary frequency). The
LANL2DZ effective core potentials and basis sets were used to
describe P, Cl, Si, and Re.33 The standard 6-31G basis set was used for
Re(CHCH-C(CMe3)C-CnC5H11)Cl(PMe2Ph)3 (8) and Re(
CH-CHC(CMe3)-CCnC5H11))Cl(PMe2Ph)3 (9). A solution of 7
(397 mg, 0.58 mmol) in hexane (15 mL) was stirred at 55 °C for 12 h.
The solvent of the reaction mixture was then removed under vacuum
at room temperature. The residue was washed with hexane (1 mL × 3)
to give a red solid, which was collected by filtration and dried under
vacuum. The red solid was identified as a mixture of 8 and 9 in a ratio
of 1:0.15 as indicated by 1H NMR. Yield: 131 mg, 33.0%. Anal. Calcd
for C38H55ClP3Re: C, 55.23; H, 6.71. Found: C, 55.44; H, 6.57.
1822
dx.doi.org/10.1021/om201184m | Organometallics 2012, 31, 1817−1824

Organometallics
Article
(3) (a) Castro-Rodrigo, R.; Esteruelas, M. A.; Lop
́
ez, A. M.; Onate, E.
̃
Table 1. Crystallographic Details for Complexes 6 and 8
Organometallics 2008, 27, 3547−3555. (b) Bolano, T.; Castarlenas, R.;
̃
6
8
Esteruelas, M. A.; Onate, E. Organometallics 2007, 26, 2037−2041.
̃
(c) Bolano, T.; Castarlenas, R.; Esteruelas, M. A.; Modrego, J.; Onate,
̃
̃
empirical formula
formula wt
T, K
C38H54Cl2P3Re
860.82
C38H55ClP3Re
826.38
E. J. Am. Chem. Soc. 2005, 127, 11184−11195. (d) Lee, J. H.; Pink, M.;
Smurnyy, Y. D.; Caulton, K. G. J. Organomet. Chem. 2008, 693, 1426−
1438.
173(2)
143(2)
wavelength, Å
cryst syst
space group
a, Å
1.5418
1.5418
(4) (a) Bannwart, E.; Jacobsen, H.; Furno, F.; Berke, H.
Organometallics 2000, 19, 3605−3619. (b) Jacobsen, H. J. Organomet.
Chem. 2003, 674, 50−55. (c) Zou, F.; Furno, F.; Fox, T.; Schmalle, H.
W.; Berke, H.; Eckert, J.; Chowdhury, Z.; Burger, P. J. Am. Chem. Soc.
2007, 129, 7195−7205.
(5) (a) Xue, W. M.; Wang, Y.; Mak, T. C. W.; Che, C. M. J. Chem.
Soc., Dalton Trans. 1996, 2827−2834. (b) Xue, W. M.; Chan, M. C.
W.; Mak, T. C. W.; Che, C. M. Inorg. Chem. 1997, 36, 6437−6439.
(c) Xue, W. M.; Wang, Y.; Chan, M. C. W.; Su, Z. M.; Cheung, K. K.;
Che, C. M. Organometallics 1998, 17, 1946−1955.
(6) (a) Williams, D. S.; Schrock, R. R. Organometallics 1994, 13,
2101−2104. (b) Vaughan, G. A.; Toreki, R.; Schrock, R. R.; Davis, W.
M. J. Am. Chem. Soc. 1993, 115, 2980−2981. (c) Toreki, R.; Vaughan,
G. A.; Schrock, R. R.; Davis, W. M. J. Am. Chem. Soc. 1993, 115, 127−
137. (d) LaPointe, A. M.; Schrock, R. R. Organometallics 1995, 14,
1875−1884. (e) Toreki, R.; Schrock, R. R.; Davis, W. M. J. Am. Chem.
Soc. 1992, 114, 3367−3380. (f) Schofield, M. H.; Schrock, R. R.; Park,
L. Y. Organometallics 1991, 10, 1844−1851. (g) Weinstock, I. A.;
Schrock, R. R.; Davis, W. M. J. Am. Chem. Soc. 1991, 113, 135−144.
(h) Toreki, R.; Schrock, R. R. J. Am. Chem. Soc. 1990, 112, 2448−
2449. (i) Schrock, R. R.; Weinstock, I. A.; Horton, A. D.; Liu, A. H.;
Schofield, M. H. J. Am. Chem. Soc. 1988, 110, 2686−2687. (j) Edwards,
D. S.; Biondi, L. V.; Ziller, J. W.; Churchill, M. R.; Schrock, R. R.
Organometallics 1983, 2, 1505−1513. (k) Edwards, D. S.; Schrock, R.
R. J. Am. Chem. Soc. 1982, 104, 6806−6808.
(7) (a) Herrmann, W. A.; Felixberger, J. K.; Anwander, R.;
Herdtweck, E.; Kiprof, P.; Riede, J. Organometallics 1990, 9, 1434−
1443. (b) Felixberger, J. K.; Kiprof, P.; Herdtweck, E.; Herrmann, W.
A.; Jakobi, R.; Gutlich, P. Angew. Chem., Int. Ed. Engl. 1989, 28, 334−
337. (c) Savage, P. D.; Wilkinson, G.; Motevalli, M.; Hursthouse, M. B.
Polyhedron 1987, 6, 1599−1601.
(8) Fischer, E. O.; Apostolidis, C.; Dornberger, E.; Filippou, A. C.;
Kanellakopulos, B.; Lungwitz, B.; Muller, J.; Powietzka, B.; Rebizant, J.;
Roth, W. Z. Naturforsch., B 1995, 50, 1382−1395.
(9) (a) Pombeiro, A. J. L.; Carvalho, M. F. N. W.; Hitchcock, P. B.;
Richrads, R. L. J. Chem. Soc., Dalton Trans. 1981, 1629−1634.
(b) Pombeiro, A. J. L.; Hughes, D. L.; Pickett, C. J.; Richards, R. L. J.
Chem. Soc., Chem. Commun. 1986, 246−247. (c) Vrtis, R. N.; Rao, C.
P.; Warner, S.; Lippard, S. J. J. Am. Chem. Soc. 1988, 110, 2669−2670.
(d) Pombeiro, A. J. L.; Hills, A.; Hughes, D. L.; Richards, R. L. J.
Organomet. Chem. 1988, 352, C5−C7. (e) Carvalho, M. F. N. N.;
Almeida, S. S. P. R.; Pombeiro, A. J. L.; Henderson, R. A.
Organometallics 1997, 16, 5441−5448.
monoclinic
P2(1)/n
19.0109(4)
19.2536(5)
21.9965(6)
90
monoclinic
P2(1)/n
9.76930(10)
10.00020(10)
38.8107(4)
90
b, Å
c, Å
α, deg
β, deg
98.130(3)
90
95.0890(10)
90
γ, deg
vol, Å3
7970.4(3)
8
3776.66(7)
4
Z
d (calcd), Mg/m3
1.435
1.453
θ range for data
collection, deg
2.88−67.50
4.57−67.50
reflns collected
47903
22740
independent reflns
13727 [R(int) =
0.0342]
6785 [R(int) = 0.0612]
data/restraints/params
goodness of fit on F2
13727/16/811
1.024
6785/0/397
1.013
final R indices [I > 2σ(I)] R1 = 0.0227, wR2 =
R1 = 0.03722, wR2 =
0.0822
0.0538
largest diff peak and hole, 0.927 and −0.399
2.133 and −0.921
e·Å−3
optimization and the larger basis set 6-311+G* was used for single-
point calculation for C and H. Polarization functionals were added for
P(ζ(d) = 0.387), Cl(ζ(d) = 0.640), Si(ζ(d) = 0.284), and Re(ζ(f) =
0.869).34 Natural bond orbital (NBO)35 analysis is also done at the
same level. All of the calculations were performed with the Gaussian
03 package.36
ASSOCIATED CONTENT
■
S
* Supporting Information
Complete ref 36, tables giving Cartesian coordinates and
electronic energies for all the calculated structures, and X-ray
crystallographic files (CIF) for 6 and 8. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: chjiag@ust.hk (G.J.), chzlin@ust.hk (Z.L.).
(10) (a) Li, X.; Schopf, M.; Stephan, J.; Kipke, J.; Harms, K.;
Sundermeyer, J. Organometallics 2006, 25, 528−530. (b) Li, X.;
Schopf, M.; Stephan, J.; Kippe, J.; Harms, K.; Sundermeyer, J. J. Am.
Chem. Soc. 2004, 126, 8660−8661. (c) Li, X.; Stephan, J.; Harms, K.;
Sundermeyer, J. Organometallics 2004, 23, 3359−3361.
(11) (a) Ozerov, O. V.; Watson, L. A.; Pink, M.; Baik, M. H.;
Caulton, K. G. Organometallics 2004, 23, 4934−4943. (b) Ozerov, O.
V.; Huffman, J. C.; Watson, L. A.; Caulton, K. G. Organometallics
2003, 22, 2539−2541. (c) Ozerov, O. V.; Pink, M.; Watson, L. A.;
Caulton, K. G. J. Am. Chem. Soc. 2004, 126, 2105−2113. (d) Ozerov,
O. V.; Watson, L. A.; Pink, M.; Caulton, K. G. J. Am. Chem. Soc. 2007,
129, 6003−6016. (e) Ozerov, O. V.; Watson, L. A.; Pink, M.; Caulton,
K. G. J. Am. Chem. Soc. 2004, 126, 6363−6378.
(12) (a) Leeaphon, M.; Fanwick, P. E.; Walton, R. A. J. Am. Chem.
Soc. 1992, 114, 1890−1892. (b) Leeaphon, M.; Ondracek, A. L.;
Thomas, R. J.; Fanwick, P. E.; Walton, R. A. J. Am. Chem. Soc. 1995,
117, 9715−9724.
(13) Chen, J.; Sung, H. H. Y.; Williams, I. D.; Lin, Z.; Jia, G. Angew.
Chem., Int. Ed. 2011, 50, 10675−10678.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the Hong Kong Research Grant
Council (Project No. HKUST601408, 602611).
REFERENCES
■
(1) See, for example: (a) Caulton, K. G. J. Organomet. Chem. 2001,
617−618, 56−64. (b) Schrock, R. R. Chem. Rev. 2002, 102, 145−179.
(c) Schrock, R. R. Chem. Commun. 2005, 2773−2777. (d) Chen, J. B.;
Wang, R. T. Coord. Chem. Rev. 2002, 231, 109−149. (e) Esteruelas, M.
́ ́
A.; Lopez, A. M.; Olivan, M. Coord. Chem. Rev. 2007, 251, 795−840.
(f) Jia, G. Coord. Chem. Rev. 2007, 251, 2167−2187.
(2) (a) Stuer, W.; Wolf, J.; Werner, H.; Schwab, P.; Schulz, M. Angew.
̈
Chem., Int. Ed. 1998, 37, 3421−3423. (b) Boone, M. P.; Brown, C. C.;
Ancelet, T. A.; Stephan, D. W. Organometallics 2010, 29, 4369−4374.
1823
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Organometallics
Article
(14) Chen, J.; He, G.; Sung, H. H. Y.; Williams, I. D.; Lin, Z.; Jia, G.
Organometallics 2010, 29, 2693−2701.
(f) Grotevendt, A. G. G.; Lummiss, J. A. M.; Mastronardi, M. L.; Fogg,
D. E. J. Am. Chem. Soc. 2011, 133, 15918−15921.
(15) Based on a search of: Cambridge Structural Database, CSD
version 5.32; August 2011.
(23) (a) Dotz, K. H.; Schafer, T.; Kroll, F.; Harms, K. Angew. Chem.,
̈
Int. Ed. Engl. 1992, 31, 1236−1238. (b) Feng, S. G.; White, P. S.;
Templeton, J. L. Organometallics 1993, 12, 2131−2139. (c) Agh-
Atabay, N. M.; Davidson, J. L.; Douglas, G.; Muir, K. W. J. Chem. Soc.,
Chem. Commun. 1989, 549−551. (d) Carnahan, E. M.; Protasiewicz, J.
D.; Lippard, S. J. Acc. Chem. Res. 1993, 26, 90−97. (e) McDermott, G.
A.; Mayr, A. J. Am. Chem. Soc. 1987, 109, 580−582. (f) Protasiewicz, J.
D.; Masschelein, A.; Lippard, S. J. J. Am. Chem. Soc. 1993, 115, 808−
810. (g) Bao, J.; Wulff, W. D.; Dominy, J. B.; Fumo, M. J.; Grant, E. B.;
Rob., A. C.; Whitcomb, M. C.; Yeung, S.-M.; Ostrander, R. L.;
Rheingold, A. L. J. Am. Chem. Soc. 1996, 118, 3392−3405. (h) Rudler,
H.; Chelain, A. E.; Goumont, D. R.; Massound, A.; Parlier, A.; Rudler,
P. M.; Yefsah, R.; Alvarez, C.; Delgado-Reyes, F. Chem. Soc. Rev. 1991,
20, 503−531. (i) Freudenberger, J. H.; Schrock, R. R. Organometallics
1986, 5, 1411−1417. (j) Strutz, H.; Dewan, J. C.; Schrock, R. R. J. Am.
Chem. Soc. 1985, 107, 5999−6005. (k) Wang, K. P.; Yun, S. Y.; Lee,
D.; Wink, D. J. J. Am. Chem. Soc. 2009, 131, 15114−15115.
(24) Bondi, A. J. Phys. Chem. 1964, 68, 441−451.
(16) Recent examples: (a) Jiang, Y.; Blaccque, O.; Fox, T.; Frech, C.
M.; Berke, H. Oganometallics 2009, 28, 4670−4680. (b) Elowe, P. R.;
West, N. M.; Labinger, J. A.; Bercaw, J. E. Organometallics 2009, 28,
6218−6227. (c) Cai, S.; Hoffman, D. M.; Wierda, D. A. Organo-
metallics 1996, 15, 1023−1032. (d) Casey, C. P.; Kraft, S.; Powell, D.
R. J. Am. Chem. Soc. 2002, 124, 2584−2594. (e) Casey, C. P.; Kraft, S.;
Powell, D. R. J. Am. Chem. Soc. 2000, 122, 3771−3772. (f) Casey, C.
P.; Strotman, N. A.; Guzei, I. A. Organometallics 2004, 23, 4121−4130.
(g) Casey, C. P.; Kraft, S.; Kavana, M. Organometallics 2001, 20,
3795−3799. (h) Casey, C. P.; Kraft, S.; Powell, D. R. Organometallics
2001, 20, 2651−2653.
(17) Usually in the range of 2.118−2.247 Å. See, for example: (a)
[CpRe(NO)(PPh3)(EtCCEt)]BF4 (2.128(9), 2.184(7) Å):
Kowalczyk, J. J.; Arif, A. M.; Gladysz, J. A. Organometallics 1991, 10,
1079−1088. (b) (η5-C9H7)Re(CO)2(MeCCMe) (2.202(12),
2.215(13) Å): Casey, C. P.; Vos, T. E.; Brady, J. T.; Hayashi, R. K.
Organometallics 2003, 22, 1183−1195. (c) [Cp*Re(CO)2(Me3CC
CCH2PMe3)]Cl (2.205(2), 2.205(2) Å): Casey, C. P.; Boller, T. M.;
Samec, J. S. M.; Reinert-Nash, J. R. Organometallics 2009, 28, 123−
131. (d) Cp*Re(CO)2(HCCCH2OH) (2.192(7), 2.163(7) Å):
Casey, C. P.; Selmeczy, A. D.; Nash, J. R.; Yi, C. S.; Powell, D. R.;
Hayashi, R. K. J. Am. Chem. Soc. 1996, 118, 6698−6706. Additional
examples: (e) Casey, C. P.; Ha, Y.; Powell, D. R. J. Organomet. Chem.
1994, 472, 185−193. (f) Einstein, F. W. B.; Tyers, K. G.; Sutton, D.
Organometallics 1985, 4, 489−493.
(25) Mo, Y.; Gao, J. Acc. Chem. Res. 2007, 40, 113−119.
(26) Douglas, P. G.; Shaw, B. L. Inorg. Synth. 1977, 17, 64−66.
(27) Shergina, S. I.; Sokolov, I. E.; Zanina, A. S. Mendeleev Commun.
1994, 4, 207.
(28) Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.;
Puschmann, H. J. Appl. Crystallogr. 2009, 42, 339−341.
(29) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112−122.
(30) Lynch, B. J.; Fast, P. L.; Harris, M.; Truhlar, D. G. J. Phys. Chem.
A 2000, 104, 4811−4815.
(31) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.;
Perderson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B 1992, 46,
6671−6687.
(18) Recent examples: (a) Uddin, M. N.; Mottalib, M. A.; Begum,
N.; Ghosh, S.; Raha, A. K.; Haworth, D. T.; Lindeman, S. V.;
Siddiquee, T. A.; Bennett, D. W.; Hogarth, G.; Nordlander, E.; Kabir,
S. E. Organometallics 2009, 28, 1514−1523. (b) Reynolds, M. A.;
Guzei, I. A.; Angelici, R. J. Chem. Commun. 2000, 513−514.
(c) Bodner, G. S.; Smith, D. E.; Hatton, W. G.; Heah, P. C.;
Georgiou, S.; Rheingold, A. L.; Geib, S. J.; Hutchinson, J. P.; Gladysz,
J. A. J. Am. Chem. Soc. 1987, 109, 7688−7705. (d) Reynolds, M. A.;
Guzei, I. A.; Angelici, R. J. J. Am. Chem. Soc. 2002, 124, 1689−1697.
(19) Hund, H. U.; Ruppli, U.; Berke, H. Helv. Chim. Acta 1993, 76,
963−975.
(32) Adamo, C.; Barone, V. J. Chem. Phys. 1998, 108, 664−675.
(33) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299−310.
(34) (a) Ehlers, A. W.; Bohme, M.; Dapprich, S.; Gobbi, A.;
̈
Hollwarth, A.; Jonas, V.; Kohler, K. F.; Stegmann, R.; Veldkamp, A.;
̈
̈
Frenking, G. Chem. Phys. Lett. 1993, 208, 111−114. (b) Hollwarth, A.;
Bohme, M.; Dapprich, S.; Ehlers, A. W.; Gobbi, A.; Jonas, V.; Kohler,
K. F.; Stegmann, R.; Veldkamp, A.; Frenking, G. Chem. Phys. Lett.
̈
̈
̈
1993, 208, 237−240.
(35) (a) Weinhold, F.; Landis, C. R. Valency and Bonding: A Natural
Bond Orbital Donor-Acceptor Perspectie; Cambridge University Press:
Cambridge, U.K., 2005. (b) Reed, A. E.; Weinstock, R. B.; Weinhold,
F. J. Chem. Phys. 1985, 83, 735−746. (c) Reed, A. E.; Weinhold, F. J.
Chem. Phys. 1985, 83, 1736−1740. (d) Reed, A. E.; Curtiss, L. A.;
Weinhold, F. Chem. Rev. 1988, 88, 899−926.
(20) For reviews on the synthetic applications of Fischer carbene
complexes, see: (a) Dotz, K. H.; Stendel, J. Jr. Chem. Rev. 2009, 109,
̈
3227−3274. (b) Dotz, K. H. Angew. Chem., Int. Ed. Engl. 1984, 23,
̈
587−608. (c) Wulff, W. D. In Comprehensive Organometallic Chemistry
II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press:
Oxford, U.K., 1995; Vol. 12, pp 469−547. (d) Hegedus, L. S. In
Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A.,
Wilkinson, G., Eds.; Pergamon Press: Oxford, U.K., 1995; Vol. 12, pp
549−576. (e) Doyle, M. In Comprehensive Organometallic Chemistry II;
Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press:
Oxford, U.K., 1995; Vol. 12, pp 387−420. (f) Harvey, D. F.; Sigano.,
D. M. Chem. Rev. 1996, 96, 271−288.
(36) Frisch, M. J.; et al. Gaussian 03, revision D.01; Gaussian, Inc.:
Wallingford, CT, 2004.
(21) (a) Masuda, T.; Sasaki, N.; Higashimura, T. Macromolecules
1975, 8, 717−721. (b) Katz, T. J.; Lee, S. J. J. Am. Chem. Soc. 1980,
102, 422−424. (c) Katz, T. J.; Lee, S. J.; Nair, M.; Savage, E. B. J. Am .
Chem. Soc. 1980, 102, 7940−7942. (d) Katz, T. J.; Hacker, S. M.;
Kendrick, R. D.; Yannoni, C. S. J. Am. Chem. Soc. 1985, 107, 2182−
2183. (e) Han, C.-C.; Katz, T. J. Organometal1ics 1985, 4, 86−2195.
(f) Levisalles, J.; Rose-Munch, F.; Rudler, H.; Daran, J.-C.; Dromzee,
Y.; Jeannin, Y.; Ades, D.; Fontanille, M. J. Chem. Soc., Chem. Commun.
1981, 1055−1057. (g) Strutz, H.; Dewan, J. C.; Schrock, R. R. J. Am.
Chem. Soc. 1985, 107, 5999−6005. (h) Landon, S. J.; Shulman, P. M.;
Geoffroy, G. L. J. Am. Chem. Soc. 1985, 107, 6539−6740.
(22) See, for example: (a) Diver, S. T.; Giessert, A. J. Chem. Rev.
2004, 104, 1317−1382. (b) Hansen, E. C.; Lee, D. Acc. Chem. Res.
2006, 39, 509−519. (c) Debleds, O.; Campagne, J. M. J. Am. Chem.
Soc. 2008, 130, 1562−1563. (d) Lee, Y. J.; Schrock, R. R.; Hoveyda, A.
H. J. Am. Chem. Soc. 2009, 131, 10652−10661. (e) Yun, S. Y.; Wang,
K. P.; Kim, M.; Lee, D. J. Am. Chem. Soc. 2010, 132, 8840−8841.
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