A Novel Pattern of Dimerization for 1,4-Diphospha-1,3-butadienes 233
FIGURE 2 ORTEP drawing of the 1,4-diphospha-1,3-butadiene 4b. [Thermal ellipsoids are drawn to the 50% probability level.]
merce and the Board of Higher Education Grant
IBHE HECA NWU 96. Use of the Advanced Pho-
ton Source was supported by the U.S. Department
of Energy, Basic Energy Sciences, Office of Energy
Research under Contract No. W-31-102-Eng-38.
The authors thank Zdzislaw Wawrzak of DND-
CAT for expert assistance with synchrotron experi-
ments.
1,2,4-Tris(2,4-di-tert-butyl-6-methyl-phenyl)-3-
(2,4-di-tert-butyl-6-methyl-phenylphosphany-
lidenemethyl)-1,2,3,4- tetrahydro-
[1,2,4]triphosphinine (5a)
The compound 5a was prepared by the same
dehydrohalogenation procedure with DBN (1,5-
diazabicyclo[4.3.0]non-5-ene) as described [12].
2-Bromo-1,5-di-tert-butyl-3-methyl-benzene (5.37 g,
0.019
mol)
and
1,2-bis(dichlorophosphino)-
methane (2.0 g, 0.0086 mol) were used for the
REFERENCES
preparation of 5a. The yield of 5a as slightly yellow
1
solid was 1.15 g (27%), with mp 124.8◦C. H NMR
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(CD2Cl2) δ = 1.06 (s, broad, 36H, t-Bu), 1.62 (s,
broad, 36H, t-Bu), 2.20 (s, 3H, Me), 2.25 (s, 3H,
Me), 2.30 (s, 3H, Me), 2.45 (s, 3H, Me), 6.1–7.95
(m, 11H, aromatic and C H protons). 31P NMR
1
3
(CDCl3) δ = −34.74 (dd, J(PP) = 197.5 Hz, J(PP)
= 37.3 Hz; (P-1)), δ = −16.97 (d,d,d, 1 J(PP) =
197.5 Hz, 2 J(PP) = 41.4 Hz, 3 J(PP) = 34.6 Hz, (P-2)),
2
3
δ = −9.04 (d,d J(PP) = 41.4 Hz, J(PP) = 37.3 Hz,
(P-3)), δ = 256.16 (d, 3 J(PP) = 34.6 Hz, (P C)). Anal.
Calcd (%) for C64H96P4: C, 77.70; H, 9.78; P, 12.52.
Found: C, 77.51; H, 9.51; P, 12.38.
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ACKNOWLEDGMENT
Portions of this work were performed at the
DuPont-Northwestern Dow Collaborative Access
Team (DND-CAT) Synchrotron Research Center lo-
cated at Sector 5 of the Advanced Photon Source
at Argonne National Laboratory. DND-CAT is sup-
ported by the E.I. DuPont de Nemours & Co., the
Dow Chemical Company, the U.S. National Science
Foundation through Grant DMR-9304725 and the
State of Illinois through the Department of Com-
[12] Appel, R.; Hu¨nerbein, J.; Siabalis, N. Angew Chem,
Int Ed 1987, 26, 779–780.