R.D. Adams et al. / Journal of Organometallic Chemistry 651 (2002) 124Á
/131
129
1
nCO (cmꢂ1 in CH2Cl2): 2054 (m), 2011 (vs). H-NMR
(d6-acetone in ppm): d 8.14 (m, 1H, Ph), 8.03 (m, 1H,
IR nCO (cmꢂ1 in CH2Cl2): 2066 (m), 2023 (s), 2015 (s,
sh), 1969 (w). 1H-NMR (d6-acetone in ppm): d 7.97 (m,
1H, Ph), 7.25 (m, 1H, Ph), 7.09 (m, 1H, Ph), 6.99 (m,
1H, Ph), 2.53 (d, 3H, Me, 2JPH 11 Hz), 2.48 (d, 3H, Me,
Ph), 7.35 (m, 1H, Ph), 6.77 (m, 1H, Ph), 2.47 (d, 3H, Me,
2
2JPH 11 Hz), 2.45 (d, 3H, Me, JPH 11 Hz), 2.17 (d, 3H,
2
2
1
2
Me, JPH 11 Hz), 1.72 (d, 3H, Me, JPH 11 Hz). H-
NMR (CDCl3 in ppm): d 8.11 (m, 1H, Ph), 7.66 (m, 1H,
Ph), 7.19 (m, 1H, Ph), 6.59 (m, 1H, Ph), 2.26 (3H, Me,
2JPH 11 Hz), 2.27 (d, 3H, Me, JPH 11 Hz), 1.96 (d, 3H,
Me, 2JPH 11 Hz). 1H-NMR (CDCl3 in ppm): d 7.96 (m,
1H, Ph), 20 (m, 1H, Ph), 6.93 (m, 1H, Ph), 6.80 (m, 1H,
2JPH 11 Hz), 2.24 (3H, Me, JPH 11 Hz), 1.93 (d, 3H,
Ph), 2.26 (3H, Me, JPH 11 Hz), 2.24 (3H, Me, JPH 11
Hz), 2.10 (d, 3H, Me, 2JPH 11 Hz), 1.86 (d, 3H, Me, 2JPH
2
2
2
Me, 2JPH 11 Hz), 1.59 (d, 3H, Me, 2JPH 11 Hz). 31P{1H}-
NMR (CDCl3 in ppm): d 314.8, ꢂ
/
12.56. Anal. Calc. C
24.41, H 1.36; Found: C 24.80, H 1.12%. Spectral Data
for 3: IR nCO (cmꢂ1 in CH2Cl2): 2061 (m), 2025 (vs). 1H-
11 Hz). 31P{1H}-NMR (CDCl3 in ppm): d 324.18, ꢂ
16.93. Anal. Calc. C 24.82, H 1.32. Found: C 25.18, H
1.20%.
/
NMR (CDCl3 in ppm): d 7.15Á
CH3), 19.52 (s, hydride),
31P{1H}-NMR (CDCl3 in ppm): d 2.35, ꢂ
3.67, ꢂ5.61, ꢂ9.50, ꢂ44.69, ꢂ48.49, ꢂ71.63. Anal.
/
7.65 (m, Ph), 0.6Á
20.18 (s, hydride).
0.80, ꢂ
/
2.2 (m,
ꢂ
/
ꢂ
/
3.6. Thermolysis of 6
/
/
/
/
/
/
/
Compound 6 (11.2 mg, 0.009 mmol) was dissolved in
15 ml of octane and brought to reflux for 30 min. After
cooling, the solvent was removed in vacuo, and the
Calc. C 28.91, H 1.71; Found: C 29.02, H 1.86%.
3.4. Thermolysis of 1
products were separated by TLC by using a 3:1 hexaneÁ
/
methylene chloride solvent mixture to yield 9.0 mg
(77%) of 2, and trace amounts of 4 and 5.
Compound 1 (35.0 mg, 0.027 mmol) was dissolved in
25 ml of octane in a three-neck flask equipped with a
reflux condenser, and then heated to reflux for 12 h.
After cooling, the solvent was removed in vacuo, and
the products were then separated by TLC by using a 3:1
3.7. Crystallographic analyses
Red single crystals of compounds 1Á
diffraction analysis were grown by slow evaporation of
solvent from a hexaneÁmethylene chloride solution at
/
6 suitable for
hexaneÁ
mg (11%) of an orangeÁ
PMe2)(m-h2-MePhPCH2)(m6-C) (4), 5.1 mg (17%) of a
brownÁred product,
/
methylene chloride solvent mixture to yield 3.7
/
red product, Ru6(CO)14(m-
/
5 8C. The crystals selected for data collection were
glued onto the ends of thin glass fibers. X-ray intensity
/
Ru6(CO)12(m-PMe2)2(m3-h2-
C6H4)(m6-C) (5), and 19.1 mg (61%) of 2. Spectral
data were measured at 293 K (1Á
/
3, 5), 183 K (4) or 173
K (6) using a Bruker SMART APEX CCD-based
Data for 4: IR nCO (cmꢂ1 in CH2Cl2): 2066 (m), 2022
(vs). 1H-NMR (CD2Cl2 in ppm): d 7.4Á
(d, 3H, Me, JPH 11 Hz), 2.23 (d, 3H, Me, JPH 11 Hz),
/
7.6 (m, Ph), 2.26
2
diffractometer using MoÁ
[13]. The raw data frames were integrated with the
program, which also applied corrections for
/
/
˚
Ka radiation (lꢁ0.71073 A)
2
2
2
1.88 (d, 3H, Me, JPH 11 Hz), 0.85 (dd, 1H, CH2, JHH
SAINT
ꢀ
/
2
2
11 Hz, JHH 7 Hz), 0.48 (d, 1H, CH2, JHH 11 Hz,
2JHH 0 Hz). 31P{1H}-NMR (CD2Cl2 in ppm): d
328.15, ꢂ48.8. Anal. Calc. C 24.25, H 1.29; Found: C
Lorentz and polarization effects. Empirical absorption
corrections based on the multiple measurement of
equivalent reflections were applied using the program
SADABS. Crystal data, data collection parameters, and
the results of the analyses are listed in Tables 1 and 2.
All structures were solved by a combination of direct
methods and difference Fourier syntheses, and refined
by full-matrix least-squares on F2, using the SHELXTL
software package [14].
Â
/
/
24.42, H 1.53%. Spectral Data for 5: IR nCO (cmꢂ1 in
CH2Cl2): 2066 (m), 2012 (vs). 1H-NMR (CDCl3 in
ppm): d 8.61 (d, 1H, Ph), 8.34 (d, 1H, Ph), 6.83 (m,
2H, Ph), 2.33 (d, 3H, Me, 2JPH 11 Hz), 2.20 (d, 3H, Me,
2JPH 11 Hz), 2.07 (d, 3H, Me, JPH 11 Hz), 1.86 (d, 3H,
Me, JPH 11 Hz). 31P{1H}-NMR (CDCl3 in ppm): d
2
2
311.32, 301.25. Anal. Calc. C 23.94, H 1.38; Found: C
24.56, H 1.23%.
Compounds 1, 2, 4 and 5 crystallized in the mono-
clinic crystal system. The space groups P21/c for 1, 2
and 4 and P21/n for 5 were identified uniquely on the
basis of the systematic absences in the intensity data and
were further confirmed by the successful solution and
refinement of the structures. Compound 1 contains two
independent formula equivalents of the complex in the
asymmetric unit. Compound 3 crystallized in the
3.5. Synthesis of Ru6(CO)14(m-PMe2)(m-h2-
Me2PC6H4)(m6-C) (6)
Compound 2 (12.3 mg, 0.010 mmol) was dissolved in
15 ml CH2Cl2. CO was then bubbled through the
solution for 3 h. The solvent was then removed in
vacuo, and the product was purified by TLC using a 3:1
¯
triclinic crystal system. The space group P1 was
/
assumed and confirmed by the successful solution and
refinement of the structure. Compound 3 contains a
hydride ligand, which was located and refined with an
isotropic thermal parameter. Compound 6 also crystal-
hexaneÁ
mg (60%) of an orangeÁ
PMe2)(m-h2-Me2PC6H4)(m6-C) (6). Spectral data for 6:
/
methylene chloride solvent mixture to yield 6.0
/
red product, Ru6(CO)14(m-
Adams, Richard D
