4438 Organometallics, Vol. 15, No. 21, 1996
Adams and Huang
data for 1 are as follows. IR (νCO in hexane, cm-1): 2099 (w,
Rea ction 4 w ith H2O. A 10.0-mg amount (0.035 mmol) of
4 and a 50.0-µL amount of distilled H2O were dissolved in 15
mL of CHCl3. The solution was heated to reflux for 22 h. After
the solvent was removed via rotary evaporation, the residue
was separated by TLC using a 2/1 hexane/CH2Cl2 solvent
mixture. This yielded the following in order of elution: 3.1
mg of 2 in 46% yield and 2.9 mg of unreacted starting material.
Con ver sion of 5 to 2. A 17.0-mg amount (0.070 mmol) of
5 was dissolved in 15 mL of heptane. The solution was heated
to reflux for 3 h. After the solvent was removed via rotary
evaporation, the residue was separated by TLC using a 2/1
hexane/CH2Cl2, solvent mixture. This yielded the following
in order of elution: 8.7 mg of 2 in 51% yield and 1.9 mg of
unreacted starting material.
br), 2005 (s), 1994 (s), 1985 (s), 1942 (s), 1749 (w, br), 1584 (w,
4
br). 1H NMR (δ in CDCl3, ppm): 6.72 (t, J H-H ) 1.0 Hz, 1H,
4
CH), 3.89 (s, 3H, OCH3), 3.86 (d, J H-H ) 1.0 Hz, 2H, CH2),
3.72 (s, 3H, OCH3). Anal. Calcd (found): C, 29.01 (28.97); H,
1.99 (2.05). MS: parent ion m/ e ) 456 (for 187Re) and ions
corresponding to the loss of each of the four carbonyl ligands.
Meth od b. In th e p r esen ce of D2O. A 54.0-µL amount
of D2O was added to a solution of a 20.0-mg amount (0.030
mmol) of Re2(CO)9(NCMe) and a 15.0-µL amount (0.096 mmol)
of MeO2C(H)CdCdC(H)CO2Me in 25 mL of hexane. The
solution was heated to reflux for 1.5 h. After the solvent was
removed in vacuo, and the residue was separated by TLC using
a
2/1 hexane/CH2Cl2, solvent mixture. This yielded the
following in order of elution: 0.7 mg of Re2(CO)10, 2.0 mg of
unreacted Re2(CO)9(NCMe), and 7.0 mg of colorless Re(CO)4-
[C(CHDCO2Me)dC(H)CO2Me] in 51% yield.
Rea ction 4 w ith EtO2CNCS. A 29.0-mg amount (0.035
mmol) of 4 and a 200.0-µL amount (1.66 mmol) of EtO2-
CNdCdS were dissolved in 10 mL of heptane. The solution
was heated to reflux for 15 h. After cooling, the solvent was
removed via rotary evaporation, and the unreacted EtO2-
CNdCdS was removed in vacuo. The residue was separated
by TLC using a 1/1 hexane/CH2Cl2, solvent mixture. This
yielded the following in order of elution: 3.9 mg of 2 in 20%
yield and 6.8 mg of orange fac-Re(CO)3(PMe2Ph)[MeO2CCH2-
CC(CO2Me)CdSN(H)CO2Et], 6, in 28% yield. Spectral data
for 6 are as follows. IR (νCO in hexane, cm-1): 2019 (vs), 1944
(s), 1914 (s), 1769 (w, br), 1740 (w, br), 1677 (w, br). 1H NMR
(δ in CDCl3, ppm): 11.60 (s, br, 1H, NH), 7.31 (m, 5H, Ph),
Rea ction of 1 w ith P Me2P h . A 10.0-mg amount (0.022
mmol) of 1 and a 4.0-µL amount (0.026 mmol) of PMe2Ph were
dissolved in 15 mL of hexane. The solution was heated to
reflux for 30 min. After cooling, the solvent was removed in
vacuo and the residue was separated by TLC using a 2/1
hexane/CH2Cl2, solvent mixture to give 12.2 mg of pale yellow
fac-Re(CO)3(PMe2Ph)[MeO2CCH2CC(H)CO2Me], 2, in 98% yield.
Spectral data for 2 are as follows. IR (νCO in hexane, cm-1):
2019 (s), 1935 (s), 1896 (s), 1740 (w, br), 1581 (w, br). 1H NMR
(δ in CDCl3, ppm): 7.40-7.30 (m, 5H, C6H5), 6.54 (m, 1H, CH),
3.70 (s, 3H, OCH3), 3.69 (m, 2H, CH2), 3.44 (s, 3H, OCH3), 1.81
2
3
4.46 (dd, J H-H ) 15.9, 2H, CH2), 4.28 (q, J H-H ) 7.1 Hz, 2H,
OCH2Me), 3.71 (s, 3H, OMe), 3.65 (s, 3H, OMe), 1.77 (d, 3J P-H
) 8.6 Hz, 3H, PMe), 1.76 (d, 3J P-H ) 8.6 Hz, 3H, PMe), 1.34 (t,
3J H-H ) 7.1 Hz, 3H, Me). Anal. Calcd (found): C, 37.93
(37.89); H, 3.62 (3.48); N, 2.01 (2.07).
3
3
(d, J P-H ) 8.4 Hz, 3H, PCH3), 1.71 (d, J P-H ) 8.4 Hz, 3H,
PCH3). MS: parent ion m/ e ) 566 plus ions corresponding
to the loss of each of the three carbonyl ligands.
Reaction of Re2(CO)9(P Me2P h ) with MeO2C(H)CdCdC-
(H)CO2Me. A 90.0-mg amount (0.12 mmol) of Re2(CO)8(PMe2-
Ph)(NCMe) and a 60.0-µL amount (0.38 mmol) of MeO2-
C(H)CdCdC(H)CO2Me were dissolved in 100 mL of hexane.
The solution was heated to reflux for 1 h. After cooling, the
solvent was removed in vacuo and the residue was separated
by TLC using a 2/1 hexane/CH2Cl2 solvent mixture. This
yielded the following in order of elution: 12.8 mg of Re2-
(CO)9(PMe2Ph), 1.5 mg of 1, 4.9 mg of pale yellow 2 (8% yield),
3.4 mg of mer-Re(CO)3(PMe2Ph)(MeO2CCH2CCHCO2Me), 5
(5% yield), 30.0 mg of mer-Re2(CO)6(PMe2Ph)[µ-η3-η1-MeO2C-
(H)CCC(H)CO2Me], 3 (31% yield), and 21.6 mg of fac-
Re2(CO)6(PMe2Ph)[µ-η3-η1-MeO2C(H)CCC(H)CO2Me], 4 (22%
yield). Spectral data for 3 are as follows. IR (νCO in hexane,
cm-1): 2045 (w), 2025 (s), 2023 (s), 1953 (s), 1946 (s), 1936
Cr ysta llogr a p h ic An a lyses. Crystals of 1 suitable for
X-ray diffraction analysis were obtained from crystallization
of a Et2O solution at -14 °C. Crystals of 3 suitable for X-ray
diffraction analysis were obtained by cooling a solution in
diethyl ether solvent to -14 °C. Crystals of 4 suitable for X-ray
diffraction analysis were obtained by slow evaporation of
solvent from a solution in a 1/1 hexane/Et2O solvent mixture
at room temperature. Crystals of 5 suitable for X-ray diffrac-
tion analysis were obtained by cooling a solution in a 1/1
hexane/Et2O solvent mixture to -20 °C. Crystals of 6 suitable
for X-ray diffraction analysis were obtained by cooling a
solution in a 1/2 hexane/Et2O solvent mixture at -20 °C. The
crystals used in intensity measurements were mounted in thin-
walled glass capillaries. Diffraction measurements were made
on a Rigaku AFC6S fully automated four-circle diffractometer
using graphite-monochromated Mo KR radiation. The unit
cells were determined and refined from 15 randomly selected
reflections obtained by using the AFC6S automatic search,
center, index, and least-squares routines. Crystal data, data
collection parameters, and results of these analyses are listed
in Table 1. All data processing was performed on a Digital
Equipment Corp. VAXstation 3520 computer or an SGI
Indigo2 computer by using the TEXSAN structure solving
program libraries obtained from the Molecular Structure
Corp., The Woodlands, TX. Neutral atom scattering factors
were calculated by the standard procedures.8a Anomalous
dispersion corrections were applied to all non-hydrogen atoms.8b
Lorentz-polarization (Lp) and absorption corrections were
applied in each analysis. Full-matrix least-squares refine-
ments minimized the following function: ∑hklw(|Fo| - |Fc|)2,
where w ) 1/σ(F)2, σ(F) ) σ(Fo2)/2Fo, and σ(Fo2) ) [σ(Iraw)2 +
(0.02Inet)2]1/2/Lp.
1
(sh), 1914 (w, br), 1900 (w, br), 1715 (w, br), 1537 (w, br). H
NMR (δ in CDCl3, ppm): 7.47 (m, 5H, Ph), 5.86 (s, 1H, CH),
5.23 (s, 1H, CH), 3.64 (s, 3H, OMe), 3.58 (s, 3H, OMe), 2.08 (d,
3
3J P-H ) 9.3 Hz, 3H, PMe), 2.01 (d, J P-H ) 9.3 Hz, 3H, PMe).
Anal. Calcd (found): C, 30.22 (30.48); H, 2.29 (2.08). Spectral
data for 4 are as follows. IR (νCO in hexane, cm-1): 2045 (s),
2020 (s), 2013 (s), 1949 (vs), 1939 (s), 1919 (w), 1898 (w, br),
1711 (w, br), 1543 (w, br). 1H NMR (δ in CDCl3, ppm): 7.45
(m, 5H, Ph), 5.65 (s, 1H, CH), 4.96 (s, 1H, CH), 3.63 (s, 3H,
3
OMe), 3.39 (s, 3H, OMe), 2.11 (d, J P-H ) 9.4 Hz, 3H, PMe),
3
2.10 (d, J P-H ) 9.4 Hz, 3H, PMe). Anal. Calcd (found): C,
30.22 (30.40); H, 2.29 (2.23). Spectral data for 5 are as follows.
IR (νCO in hexane, cm-1): 2041 (w, br), 1940 (s), 1899 (m), 1747
(w, br), 1577 (w, br). 1H NMR (δ in CDCl3, ppm): 7.58-7.36
(m, 5H, Ph), 6.59 (m, 1H, CH), 3.99 (m, 2H, CH2), 3.72 (s, 3H,
3
OMe), 3.68 (s, 3H, OMe), 1.98 (d, J P-H ) 8.0 Hz, 6H, PMe2).
Anal. Calcd (found): C, 38.23 (38.42); H, 3.56 (3.33).
Con ver sion of 3 to 4. Meth od a . A 5.0-mg amount of 3
and 0.6 mL of CDCl3 were placed in a 5-mm NMR tube at room
temperature. Compound 3 was slowly transformed to 4. After
7 days, the 4/3 ratio was 2/1, as determined by 1H NMR
spectroscopy.
Compounds 1, 3, and 5 crystallized in the triclinic crystal
system. The space group P1h was assumed and confirmed in
each case by the successful solution and refinement of the
structures. The structures were solved by a combination of
Meth od b. A 5.0-mg amount of 4 and 0.6 mL of CDCl3 were
placed in a 5-mm NMR tube at room temperature. The
transformation was monitored by 1H NMR spectroscopy. After
7 days, the formation of 3 was not detected.
(8) (a) International Tables for X-ray Crystallography; Kynoch
Press: Birmingham, England, 1975; Vol. IV, Table 2.2B, pp 99-101.
(b) Ibid., Table 2.3.1, pp 149-150.