226
T.M.A. Al-Shboul et al. / Journal of Organometallic Chemistry 696 (2011) 216e227
4.13. Synthesis of 3,6-bis(diphenylphosphanyl)-2,2,7,7-
tetrametylocta-3,5-diene (3tBu) and 3,6-bis(diphenylphosphanyl)-
2,2,7,7-tetrametylocta-3,4-diene (5)
in combination with the resolution of identity (`RI`) density fitting
technique [57]. Molecular structures were visualized with the
Pymol program [58]. Reaction energies have not been corrected for
basis set superposition effects.
2,2,7,7-Tetramethyl-3,5-octadiyne (0.20 g, 1.23 mmol) was dis-
solved in 15 ml of THF at ꢀ78 ꢁC. HPPh2 (0.43 ml, 2.46 mmol) and
5 mol-% of [(thf)4Ca(PPh2)2] (1) were added, and the solution was
stirred at room temperature for two hours. Then the volume was
reduced to half of the original volume and 7 ml of methanol were
added. After 3 days a mixture of (Z,Z)-3tBu and 5 was obtained at
room temperature (0.91 g, 69%). The physical data of 5 were
determined from crystalline material, whereas (Z,Z)-3tBu was
always contaminated with 5.
Acknowledgement
We thank the Deutsche Forschungsgemeinschaft (DFG, Bonn/
Germany) for generous financial support of this research initiative.
We also gratefully acknowledge the funding of the Fonds der
Chemischen Industrie (Frankfurt/Main, Germany) and of the Frie-
drich-Schiller-Universität (Jena, Germany).
Appendix A. Supporting information
4.14. Physical data of (Z,Z)-3tBu
Crystallographic data (excluding structure factors) has been
deposited with the Cambridge Crystallographic Data Centre as
supplementary publication CCDC-779117 for 2b, CCDC-779118 for
1H NMR (200.13 MHz, CDCl3):
7.1e7.5 (Ph). d
31P NMR (81.013 MHz, CDCl3):
d
¼ 0.93 (tBu), 7.01 (C]CH),
¼ ꢀ5.6.
d
¼
3
Me, CCDC-779119 for 3Silyl, CCDC-779120 for 3Mes, CCDC-779121
4.15. Physical data of 5
for 4, and CCDC-779122 for 5. Copies of the data can be obtained
free of charge on application to CCDC, 12 Union Road, Cambridge
M.p. 148e151 ꢁC. MS (EI): 534 [M]þ (1%), 477 [MetBu]þ, 349
[MePPh2]þ (100%), 293 [349-tBu]þ (20%),183 [PPh2e2H]þ (60%). 1H
NMR (200.13 MHz, CDCl3):
J ¼ 8.7, 5.3 Hz), 4.68 (1H, ddd, J ¼ 16.5, 8.3, 2.4 Hz), 6.92e7.43
(phenyl). 13C{1H} NMR (50.328 MHz, CDCl3):
d
¼ 1.02 (9H, s), 1.3 (9H, s), 2.88 (1H, dd,
References
d
¼ 29.0 (J ¼ 9.7), 29.4
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(J ¼ 16.7 Hz), 90.1 (J ¼ 3.6 Hz), 127.5 (J ¼ 7.3 Hz), 128.1 (J ¼ 6.1 Hz),
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